Microbiocidal quinoline (thio)carboxamide derivatives

ABSTRACT

Compounds of the formula (I) wherein the subsitiuents are as defined in claim 1. Furthermore, the present invention relates to agrochemical compositions which comprise compounds of formula (I), to preparation of these compositions, and to the use of the compounds or compositions in agriculture or horticulture for combating, preventing or controlling infestation of plants, harvested food crops, seeds or non-living materials by phytopathogenic microorganisms, in particular fungi.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a 371 National Stage application of InternationalApplication No. PCT/EP2018/074479 filed Sep. 11, 2018 which claimspriority to EP 17190905.4, filed Sep. 13, 2017, the entire contents ofwhich applications are hereby incorporated by reference.

The present invention relates to microbiocidal quinoline(thio)carboxamide derivatives, e.g. as active ingredients, which havemicrobiocidal activity, in particular fungicidal activity. The inventionalso relates to preparation of these quinoline (thio)carboxamidederivatives, to intermediates useful in the preparation of thesequinoline (thio)carboxamide derivatives, to the preparation of theseintermediates, to agrochemical compositions which comprise at least oneof the quinoline (thio)carboxamide derivatives, to preparation of thesecompositions and to the use of the quinoline (thio)carboxamidederivatives or compositions in agriculture or horticulture forcontrolling or preventing infestation of plants, harvested food crops,seeds or non-living materials by phytopathogenic microorganisms, inparticular fungi.

Certain fungicidal quinoline (thio)carboxamide compounds are describedin WO04039783.

It has now surprisingly been found that certain novel quinoline(thio)carboxamide derivatives have favourable fungicidal properties.

The present invention therefore provides compounds of formula (I)

wherein

X is O or S;

R₁ is hydrogen, halogen, methyl, or cyano;

R₂ is hydrogen, methyl or halogen;

R₃ and R₄ are each independently selected from hydrogen, halogen ormethyl;

R₅ is C₁-C₆ alkyl, C₂-C₆ alkenyl, C₃-C₇ cycloalkyl or C₃-C₄cycloalkyl(C₁-C₃)alkyl, wherein the alkyl, alkenyl and cycloalkyl groupsmay be optionally substituted with 1 to 3 substituents independentlyselected from halogen, cyano, C₁-C₃ alkyl, C₁-C₃ alkoxy and C₁-C₃alkylthio;

R₆ is hydrogen, cyano or C₁-C₄ alkyl, wherein the alkyl may beoptionally substituted with 1 to 3 substituents independently selectedfrom halogen and C₁-C₃ alkoxy;

R₇ is hydrogen, C₁-C₅ alkyl, C₃-C₇ cycloalkyl, (C₁-C₃ alkyl)₃silyl,phenyl or thiophenyl, wherein the alkyl and cycloalkyl may be optionallysubstituted with one to three substituents independently selected fromhalogen, cyano, C₁-C₃ alkyl, C₁-C₃ alkoxy and C₁-C₃ alkylthio, andwherein the phenyl and thiophenyl may be optionally substituted with oneto three substituents independently selected from halogen, C₁-C₃ alkyl,C₁-C₃ haloalkyl and C₁-C₃ alkoxy;

A is a direct bond or C(R₈)(R₉);

R₈ and R₉ are independently selected from hydrogen, fluoro and methyl;and salts, enantiomers and/or N-oxides thereof, provided the compound isnot

In a second aspect the present invention provides an agrochemicalcomposition comprising a compound of formula (I).

Compounds of formula (I) may be used to control phytopathogenicmicroorganisms. Thus, in order to control a phytopathogen a compound offormula (I), or a composition comprising a compound of formula (I),according to the invention may be applied directly to the phytopathogen,or to the locus of a phytopathogen, in particular to a plant susceptibleto attack by phytopathogens.

Thus, in a third aspect the present invention provides the use of acompound of formula (I), or a composition comprising a compound offormula (I), as described herein to control a phytopathogen.

In a further aspect the present invention provides a method ofcontrolling phytopathogens, comprising applying a compound of formula(I), or a composition comprising a compound of formula (I), as describedherein to said phytopathogen, or to the locus of said phytopathogen, inparticular to a plant susceptible to attack by a phytopathogen.

Compounds of formula (I) are particularly effective in the control ofphytopathogenic fungi.

Thus, in a yet further aspect the present invention provides the use ofa compound of formula (I), or a composition comprising a compound offormula (I), as described herein to control phytopathogenic fungi.

In a further aspect the present invention provides a method ofcontrolling phytopathogenic fungi, comprising applying a compound offormula (I), or a composition comprising a compound of formula (I), asdescribed herein to said phytopathogenic fungi, or to the locus of saidphytopathogenic fungi, in particular to a plant susceptible to attack byphytopathogenic fungi.

Where substituents are indicated as being optionally substituted, thismeans that they may or may not carry one or more identical or differentsubstituents, e.g. one to four substituents. Normally not more thanthree such optional substituents are present at the same time.Preferably not more than two such optional substituents are present atthe same time (i.e. the group may be optionally substituted by one ortwo of the substituents indicated as “optional”). Where the “optionalsubstituent” group is a larger group, such as cycloalkyl or phenyl, itis most preferred that only one such optional substituent is present.Where a group is indicated as being substituted, e.g. alkyl, thisincludes those groups that are part of other groups, e.g. the alkyl inalkylthio.

The term “halogen” refers to fluorine, chlorine, bromine or iodine,preferably fluorine, chlorine or bromine.

Alkyl substituents (either alone or as part of a larger group, such asalkoxy-, alkylthio-) may be straight-chained or branched. Alkyl on itsown or as part of another substituent is, depending upon the number ofcarbon atoms mentioned, for example, methyl, ethyl, n-propyl, n-butyl,n-pentyl, n-hexyl and the isomers thereof, for example, iso-propyl,iso-butyl, sec-butyl, tert-butyl or iso-amyl.

Alkenyl substituents (either alone or as part of a larger group, e.g.alkenyloxy) can be in the form of straight or branched chains, and thealkenyl moieties, where appropriate, can be of either the (E)- or(Z)-configuration. Examples are vinyl and allyl. The alkenyl groups arepreferably C₂-C₆, more preferably C₂-C₄ and most preferably C₂-C₃alkenyl groups.

Alkynyl substituents (either alone or as part of a larger group, e.g.alkynyloxy) can be in the form of straight or branched chains. Examplesare ethynyl and propargyl. The alkynyl groups are preferably C₂-C₆, morepreferably C₂-C₄ and most preferably C₂-C₃ alkynyl groups.

Cycloalkyl substituents may be saturated or partially unsaturated,preferably fully saturated, and are, for example, cyclopropyl,cyclobutyl, cyclopentyl or cyclohexyl.

Haloalkyl groups (either alone or as part of a larger group, e.g.haloalkyloxy) may contain one or more identical or different halogenatoms and, for example, may stand for CH₂Cl, CHCl₂, CCl₃, CH₂F, CHF₂,CF₃, CF₃CH₂, CH₃CF₂, CF₃CF₂ or CCl₃CCl₂.

Haloalkenyl groups (either alone or as part of a larger group, e.g.haloalkenyloxy) are alkenyl groups, respectively, which are substitutedwith one or more of the same or different halogen atoms and are, forexample, 2,2-difluorovinyl or 1,2-dichloro-2-fluoro-vinyl.

Haloalkynyl groups (either alone or as part of a larger group, e.g.haloalkynyloxy) are alkynyl groups, respectively, which are substitutedwith one or more of the same or different halogen atoms and are, forexample, 1-chloro-prop-2-ynyl.

Alkoxy means a radical —OR, where R is alkyl, e.g. as defined above.Alkoxy groups include, but are not limited to, methoxy, ethoxy,1-methylethoxy, propoxy, butoxy, 1-methylpropoxy and 2-methylpropoxy.

Cyano means a —CN group.

Amino means an —NH₂ group.

Hydroxyl or hydroxy stands for a —OH group.

Aryl groups (either alone or as part of a larger group, such as e.g.aryloxy, aryl-alkyl) are aromatic ring systems which can be in mono-,bi- or tricyclic form. Examples of such rings include phenyl, naphthyl,anthracenyl, indenyl or phenanthrenyl. Preferred aryl groups are phenyland naphthyl, phenyl being most preferred. Where an aryl moiety is saidto be substituted, the aryl moiety is preferably substituted by one tofour substituents, most preferably by one to three substituents.

Heteroaryl groups (either alone or as part of a larger group, such ase.g. heteroaryloxy, heteroaryl-alkyl) are aromatic ring systemscontaining at least one heteroatom and consisting either of a singlering or of two or more fused rings. Preferably, single rings willcontain up to three heteroatoms and bicyclic systems up to fourheteroatoms which will preferably be chosen from nitrogen, oxygen andsulfur. Examples of monocyclic groups include pyridyl, pyridazinyl,pyrimidinyl, pyrazinyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl (e.g.[1,2,4] triazolyl), furanyl, thiophenyl, oxazolyl, isoxazolyl,oxadiazolyl, thiazolyl, isothiazolyl and thiadiazolyl. Examples ofbicyclic groups include purinyl, quinolinyl, cinnolinyl, quinoxalinyl,indolyl, indazolyl, benzimidazolyl, benzothiophenyl and benzothiazolyl.Monocyclic heteroaryl groups are preferred, pyridyl being mostpreferred. Where a heteroaryl moiety is said to be substituted, theheteroaryl moiety is preferably substituted by one to four substituents,most preferably by one to three substituents.

Heterocyclyl groups, heterocycles or heterocyclic rings (either alone oras part of a larger group, such as heterocyclyl-alkyl) are non-aromaticring structures containing up to 10 atoms including one or more(preferably one, two or three) heteroatoms selected from O, S and N.Examples of monocyclic groups include, oxetanyl, 4,5-dihydro-isoxazolyl,thietanyl, pyrrolidinyl, tetrahydrofuranyl, [1,3]dioxolanyl,piperidinyl, piperazinyl, [1,4]dioxanyl, imidazolidinyl,[1,3,5]oxadiazinanyl, hexahydro-pyrimidinyl, [1,3,5]triazinanyl andmorpholinyl or their oxidised versions such as 1-oxo-thietanyl and1,1-dioxo-thietanyl. Examples of bicyclic groups include2,3-dihydro-benzofuranyl, benzo[1,4]dioxolanyl, benzo[1,3]dioxolanyl,chromenyl, and 2,3-dihydro-benzo[1,4]dioxinyl. Where a heterocyclylmoiety is said to be substituted, the heterocyclyl moiety is preferablysubstituted by one to four substituents, most preferably by one to threesubstituents.

The presence of one or more possible asymmetric carbon atoms in acompound of formula (I) means that the compounds may occur in opticallyisomeric forms, i.e. enantiomeric or diastereomeric forms. Alsoatropisomers may occur as a result of restricted rotation about a singlebond. Formula (I) is intended to include all those possible isomericforms and mixtures thereof. The present invention includes all thosepossible isomeric forms and mixtures thereof for a compound of formula(I). Likewise, formula (I) is intended to include all possibletautomers. The present invention includes all possible tautomeric formsfor a compound of formula (I).

In each case, the compounds of formula (I) according to the inventionare in free form, in oxidized form as a N-oxide or in salt form, e.g. anagronomically usable salt form.

N-oxides are oxidized forms of tertiary amines or oxidized forms ofnitrogen containing heteroaromatic compounds. They are described forinstance in the book “Heterocyclic N-oxides” by A. Albini and S. Pietra,CRC Press, Boca Raton 1991.

Preferred values of X, R₁, R₂, R₃, R₄, R₅, R₆, R₇ and A are, in anycombination thereof, as set out below:

Preferably X is O.

Preferably R₁ is hydrogen, fluoro, chloro, methyl or cyano.

More preferably R₁ is hydrogen, fluoro, chloro or methyl.

Most preferably R₁ is fluoro, chloro or methyl.

Preferably R₂ is hydrogen, methyl, chloro or fluoro.

More preferably R₂ is hydrogen, chloro or fluoro.

Most preferably R₂ is hydrogen or fluoro.

Preferably R₃ and R₄ are each independently selected from hydrogen andmethyl.

More preferably R₃ is methyl and R₄ is hydrogen; or R₃ is hydrogen andR₄ is methyl; or R₃ is hydrogen and R₄ is hydrogen.

Most preferably R₃ and R₄ are both hydrogen.

Preferably R₅ is C₁-C₆ alkyl, C₂-C₆ alkenyl, cyclopropyl or C₃-C₄cycloalkyl-CH₂—, wherein the alkyl, alkenyl and cycloalkyl groups may beoptionally substituted with 1 to 3 substituents independently selectedfrom fluoro, chloro and methyl.

More preferably R₅ is C₁-C₅ alkyl, C₂-C₄ alkenyl, cyclopropyl or C₃-C₄cycloalkyl-CH₂—, wherein the alkyl, alkenyl and cycloalkyl groups may beoptionally substituted with 1 to 3 fluoro or one methyl.

Most preferably R₅ is ethyl, isopropyl, tert-butyl, isopropenyl orcyclopropyl, wherein the ethyl, isopropyl and cyclopropyl groups may beoptionally substituted with 1 to 3 fluoro or one methyl when A is adirect bond, or R₅ is ethyl, propyl, isobutyl, neo-pentyl, C₃-C₄ alkenylor cyclopropyl-CH₂—, wherein the ethyl, propyl, isobutyl, neo-pentyl,C₃-C₄ alkenyl and cyclopropyl groups may be optionally substituted with1 to 3 fluoros or one methyl when A is CH₂.

Preferably R₆ is hydrogen or C₁-C₂ alkyl, wherein the alkyl may beoptionally substituted with 1 to 3 substituents independently selectedfrom fluoro and methoxy.

More preferably R₆ is hydrogen, methyl or ethyl.

Most preferably R₆ is hydrogen or methyl.

Preferably R₇ is C₁-C₄ alkyl, C₃-C₆ cycloalkyl, phenyl or thiophenyl,wherein the alkyl and cycloalkyl may be optionally substituted with oneto three substituents independently selected from fluoro, chloro, methyland methoxy, and wherein the phenyl and thiophenyl may be optionallysubstituted with one to three substituents independently selected fromfluoro, chloro, trifluoromethyl, methyl and methoxy when A is a directbond, or R₇ is C₁-C₄ alkyl, C₃-C₆ cycloalkyl, trimethylsilyl, phenyl orthiophenyl, wherein the alkyl and cycloalkyl may be optionallysubstituted with one to three substituents independently selected fromfluoro, chloro, methyl and methoxy, and wherein the phenyl andthiophenyl may be optionally substituted with one to three substituentsindependently selected from fluoro, chloro, trifluoromethyl, methyl andmethoxy when A is CH₂.

More preferably R₇ is phenyl or thiophenyl, wherein the phenyl andthiophenyl may be optionally substituted with one to three substituentsindependently selected from fluoro, chloro and methyl when A is a directbond, or R₇ is C₁-C₄ alkyl, cyclopropyl, cyclobutyl, phenyl orthiophenyl, wherein the alkyl cyclopropyl and cyclobutyl may beoptionally substituted with one to three fluoro substituents or onemethyl when A is CH₂.

Most preferably R₇ is phenyl or thiophenyl when A is a direct bond, orR₇ is methyl, ethyl, isopropyl, cyclopropyl or cyclobutyl, wherein themethyl, ethyl, isopropyl, cyclopropyl and cyclobutyl may be optionallysubstituted with one to three fluoro substituents or one methyl when Ais CH₂.

Preferably A is a direct bond or CH₂.

More preferably A is a direct bond and R₇ is C₁-C₄ alkyl, C₃-C₆cycloalkyl, phenyl or thiophenyl, wherein the alkyl and cycloalkyl maybe optionally substituted with one to three substituents independentlyselected from fluoro, chloro, methyl and methoxy, and wherein the phenyland thiophenyl may be optionally substituted with one to threesubstituents independently selected from fluoro, chloro,trifluoromethyl, methyl and methoxy; or, alternatively, A is CH₂ and R₇is C₁-C₄ alkyl, C₃-C₆ cycloalkyl, trimethylsilyl, phenyl or thiophenyl,wherein the alkyl and cycloalkyl may be optionally substituted with oneto three substituents independently selected from fluoro, chloro, methyland methoxy, and wherein the phenyl and thiophenyl may be optionallysubstituted with one to three substituents independently selected fromfluoro, chloro, trifluoromethyl, methyl and methoxy.

Even more preferably A is a direct bond and R₇ is phenyl or thiophenyl,wherein the phenyl and thiophenyl may be optionally substituted with oneto three substituents independently selected from fluoro, chloro andmethyl; or, alternatively, A is CH₂ and R₇ is C₁-C₄ alkyl, cyclopropyl,cyclobutyl, phenyl or thiophenyl, wherein the alkyl cyclopropyl andcyclobutyl may be optionally substituted with one to three fluorosubstituents or one methyl.

Most preferably A is a direct bond and R₅ is ethyl, isopropyl,tert-butyl, isopropenyl or cyclopropyl, wherein the ethyl, isopropyl andcyclopropyl groups may be optionally substituted with 1 to 3 fluoro orone methyl and R₇ is phenyl or thiophenyl; or, alternatively, A is CH₂and R₅ is ethyl, propyl, isobutyl, neo-pentyl, C₃-C₄ alkenyl orcyclopropyl-CH₂—, wherein the ethyl, propyl, isobutyl, neo-pentyl, C₃-C₄alkenyl and cyclopropyl groups may be optionally substituted with 1 to 3fluoros or one methyl and R₇ is methyl, ethyl, isopropyl, cyclopropyl orcyclobutyl, wherein the methyl, ethyl, isopropyl, cyclopropyl andcyclobutyl may be optionally substituted with one to three fluorosubstituents or one methyl.

Embodiments according to the invention are provided as set out below.

Embodiment 1 provides compounds of formula (I), or a salt, enantiomer orN-oxide thereof, as defined above.

Embodiment 2 provides compounds according to embodiment 1, or a salt,enantiomer or N-oxide thereof, wherein R₁ is hydrogen, fluoro, chloro,methyl or cyano.

Embodiment 3 provides compounds according to embodiment 1 or 2, or asalt, enantiomer or N-oxide thereof, wherein R₂ is hydrogen, methyl,chloro or fluoro.

Embodiment 4 provides compounds according to any one of embodiments 1, 2or 3, or a salt, enantiomer or N-oxide thereof, wherein R₃ and R₄ areeach independently selected from hydrogen and methyl.

Embodiment 5 provides compounds according to any one of embodiments 1,2, 3 or 4, or a salt, enantiomer or N-oxide thereof, wherein R₅ is C₁-C₆alkyl, C₂-C₆ alkenyl, cyclopropyl or C₃-C₄cycloalkyl-CH₂—, wherein thealkyl, alkenyl and cycloalkyl groups may be optionally substituted with1 to 3 substituents independently selected from fluoro, chloro andmethyl.

Embodiment 6 provides compounds according to any one of embodiments 1,2, 3, 4, or 5, or a salt, enantiomer or N-oxide thereof, wherein R₆ ishydrogen or C₁-C₂ alkyl, wherein the alkyl may be optionally substitutedwith 1 to 3 substituents independently selected from fluoro and methoxy.

Embodiment 7 provides compounds according to any one of embodiments 1,2, 3, 4, 5, or 6, or a salt, enantiomer or N-oxide thereof, wherein A isa direct bond or CH₂.

Embodiment 8 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, or 7, or a salt, enantiomer or N-oxide thereof, whereinR₇ is C₁-C₄ alkyl, C₃-C₆ cycloalkyl, phenyl or thiophenyl, wherein thealkyl and cycloalkyl may be optionally substituted with one to threesubstituents independently selected from fluoro, chloro, methyl andmethoxy, and wherein the phenyl and thiophenyl may be optionallysubstituted with one to three substituents independently selected fromfluoro, chloro, trifluoromethyl, methyl and methoxy when A is a directbond, or R₇ is C₁-C₄ alkyl, C₃-C₆ cycloalkyl, trimethylsilyl, phenyl orthiophenyl, wherein the alkyl and cycloalkyl may be optionallysubstituted with one to three substituents independently selected fromfluoro, chloro, methyl and methoxy, and wherein the phenyl andthiophenyl may be optionally substituted with one to three substituentsindependently selected from fluoro, chloro, trifluoromethyl, methyl andmethoxy when A is CH₂.

Embodiment 9 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, or 8, or a salt, enantiomer or N-oxide thereof,wherein R₁ is hydrogen, fluoro, chloro or methyl.

Embodiment 10 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, or 9, or a salt, enantiomer or N-oxide thereof,wherein R₂ is hydrogen, chloro or fluoro.

Embodiment 11 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9 or 10, or a salt, enantiomer or N-oxide thereof,wherein R₃ is methyl and R₄ is hydrogen; or R₃ is hydrogen and R₄ ismethyl; or R₃ is hydrogen and R₄ is hydrogen.

Embodiment 12 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10 or 11, or a salt, enantiomer or N-oxidethereof, wherein R₅ is C₁-C₅ alkyl, C₂-C₄ alkenyl, cyclopropyl orC₃-C₄cycloalkyl-CH₂—, wherein the alkyl, alkenyl and cycloalkyl groupsmay be optionally substituted with 1 to 3 fluoro or one methyl.

Embodiment 13 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, or a salt, enantiomer or N-oxidethereof, wherein R₆ is hydrogen, methyl or ethyl.

Embodiment 14 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 or 13, or a salt, enantiomer orN-oxide thereof, wherein R₇ is phenyl or thiophenyl, wherein the phenyland thiophenyl may be optionally substituted with one to threesubstituents independently selected from fluoro, chloro and methyl whenA is a direct bond, or R₇ is C₁-C₄ alkyl, cyclopropyl, cyclobutyl,phenyl or thiophenyl, wherein the alkyl cyclopropyl and cyclobutyl maybe optionally substituted with one to three fluoro substituents or onemethyl when A is CH₂.

Embodiment 15 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14, or a salt, enantiomer orN-oxide thereof, wherein R₁ is fluoro, chloro or methyl.

Embodiment 16 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15, or a salt, enantiomeror N-oxide thereof, wherein R₂ is hydrogen or fluoro.

Embodiment 17 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 or 16, or a salt,enantiomer or N-oxide thereof, wherein R₃ and R₄ are both hydrogen.

Embodiment 18 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16 or 17, or a salt,enantiomer or N-oxide thereof, wherein R₅ is ethyl, isopropyl,tert-butyl, isopropenyl or cyclopropyl, wherein the ethyl, isopropyl andcyclopropyl groups may be optionally substituted with 1 to 3 fluoro orone methyl when A is a direct bond, or R₅ is ethyl, propyl, isobutyl,neo-pentyl, C₃-C₄ alkenyl or cyclopropyl-CH₂—, wherein the ethyl,propyl, isobutyl, neo-pentyl, C₃-C₄ alkenyl and cyclopropyl groups maybe optionally substituted with 1 to 3 fluoros or one methyl when A isCH₂.

Embodiment 19 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17 or 18, or a salt,enantiomer or N-oxide thereof, wherein R₆ is hydrogen or methyl.

Embodiment 20 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18 or 19, or asalt, enantiomer or N-oxide thereof, wherein R₇ is phenyl or thiophenylwhen A is a direct bond, or R₇ is methyl, ethyl, isopropyl, cyclopropylor cyclobutyl, wherein the methyl, ethyl, isopropyl, cyclopropyl andcyclobutyl may be optionally substituted with one to three fluorosubstituents or one methyl when A is CH₂.

Embodiment 21 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20, ora salt, enantiomer or N-oxide thereof, wherein X is O.

Embodiment 22 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20, ora salt, enantiomer or N-oxide thereof, wherein X is S.

One group of compounds according to the invention are those of formula(I′):

wherein R₁, R₂, R₃, R₄, R₅, R₆, R₇ and A are as defined for compounds offormula (I), or a salt, enantiomer or N-oxide thereof. Preferreddefinitions of R₁, R₂, R₃, R₄, R₅, R₆, R₇ and A are as defined forcompounds of formula (I).

One preferred group of compounds of formula (I′) are those of formula(I′A):

wherein R₁, R₂, R₃, R₄, R₅, R₆ and R₇ are as defined for compounds offormula (I), or a salt, enantiomer or N-oxide thereof. Preferreddefinitions of R₁, R₂, R₃, R₄, R₅, R₆ and R₇ are as defined forcompounds of formula (I).

Another preferred group of compounds of formula (I′) are those offormula (I′B):

wherein R₁, R₂, R₃, R₄, R₅, R₆ and R₇ are as defined for compounds offormula (I), or a salt, enantiomer or N-oxide thereof. Preferreddefinitions of R₁, R₂, R₃, R₄, R₅, R₆ and R₇ are as defined forcompounds of formula (I).

One group of compounds according to the invention are those of formula(I″):

wherein R₁, R₂, R₃, R₄, R₅, R₆, R₇ and A are as defined for compounds offormula (I), or a salt, enantiomer or N-oxide thereof. Preferreddefinitions of R₁, R₂, R₃, R₄, R₅, R₆, R₇ and A are as defined forcompounds of formula (I).

One preferred group of compounds of formula (I″) are those of formula(I″A):

wherein R₁, R₂, R₃, R₄, R₅, R₆ and R₇ are as defined for compounds offormula (I), or a salt, enantiomer or N-oxide thereof. Preferreddefinitions of R₁, R₂, R₃, R₄, R₅, R₆ and R₇ are as defined forcompounds of formula (I).

Another preferred group of compounds of formula (I″) are those offormula (I″B):

wherein R₁, R₂, R₃, R₄, R₅, R₆ and R₇ are as defined for compounds offormula (I), or a salt, enantiomer or N-oxide thereof. Preferreddefinitions of R₁, R₂, R₃, R₄, R₅, R₆ and R₇ are as defined forcompounds of formula (I).

A preferred group of compounds according to the invention are those offormula (I-1) which are compounds of formula (I) wherein X is O or S; R₁is hydrogen, fluoro, chloro, methyl or cyano; R₂ is hydrogen, methyl,chloro or fluoro; R₃ and R₄ are each independently selected fromhydrogen and methyl; R₅ is C₁-C₆ alkyl, C₂-C₆ alkenyl, cyclopropyl orC₃-C₄ cycloalkyl-CH₂—, wherein the alkyl, alkenyl and cycloalkyl groupsmay be optionally substituted with 1 to 3 substituents independentlyselected from fluoro, chloro and methyl; R₆ is hydrogen or C₁-C₂ alkyl,wherein the alkyl may be optionally substituted with 1 to 3 substituentsindependently selected from fluoro and methoxy; A is a direct bond andR₇ is C₁-C₄ alkyl, C₃-C₆ cycloalkyl, phenyl or thiophenyl, wherein thealkyl and cycloalkyl may be optionally substituted with one to threesubstituents independently selected from fluoro, chloro, methyl andmethoxy, and wherein the phenyl and thiophenyl may be optionallysubstituted with one to three substituents independently selected fromfluoro, chloro, trifluoromethyl, methyl and methoxy; or, alternatively,A is CH₂ and R₇ is C₁-C₄ alkyl, C₃-C₆ cycloalkyl, trimethylsilyl, phenylor thiophenyl, wherein the alkyl and cycloalkyl may be optionallysubstituted with one to three substituents independently selected fromfluoro, chloro, methyl and methoxy, and wherein the phenyl andthiophenyl may be optionally substituted with one to three substituentsindependently selected from fluoro, chloro, trifluoromethyl, methyl andmethoxy; or a salt, enantiomer or N-oxide thereof.

One group of compounds according to this embodiment are compounds offormula (I-1a) which are compounds of formula (I-1) wherein X is O.

Another group of compounds according to this embodiment are compounds offormula (I-1b) which are compounds of formula (I-1) wherein X is S.

A further preferred group of compounds according to the invention arethose of formula (I-2) which are compounds of formula (I) wherein X is Oor S; R₁ is hydrogen, fluoro, chloro or methyl; R₂ is hydrogen, chloroor fluoro; R₃ is methyl and R₄ is hydrogen; or R₃ is hydrogen and R₄ ismethyl; or R₃ is hydrogen and R₄ is hydrogen; R₅ is C₁-C₅ alkyl, C₂-C₄alkenyl, cyclopropyl or C₃-C₄cycloalkyl-CH₂—, wherein the alkyl, alkenyland cycloalkyl groups may be optionally substituted with 1 to 3 fluoroor one methyl; R₆ is hydrogen methyl or ethyl; A is a direct bond and R₇is phenyl or thiophenyl, wherein the phenyl and thiophenyl may beoptionally substituted with one to three substituents independentlyselected from fluoro, chloro and methyl; or, alternatively, A is CH₂ andR₇ is C₁-C₄ alkyl, cyclopropyl, cyclobutyl, phenyl or thiophenyl,wherein the alkyl cyclopropyl and cyclobutyl may be optionallysubstituted with one to three fluoro substituents or one methyl; or asalt, enantiomer or N-oxide thereof.

One group of compounds according to this embodiment are compounds offormula (I-2a) which are compounds of formula (I-2) wherein X is O.

Another group of compounds according to this embodiment are compounds offormula (I-2b) which are compounds of formula (I-2) wherein X is S.

A further preferred group of compounds according to the invention arethose of formula (I-3) which are compounds of formula (I) wherein X is Oor S; R₁ is fluoro, chloro or methyl; R₂ is hydrogen or fluoro; R₃ andR₄ are both hydrogen; R₆ is hydrogen or methyl; A is a direct bond andR₅ is ethyl, isopropyl, tert-butyl, isopropenyl or cyclopropyl, whereinthe ethyl, isopropyl and cyclopropyl groups may be optionallysubstituted with 1 to 3 fluoro or one methyl and R₇ is phenyl orthiophenyl; or, alternatively, A is CH₂ and R₅ is ethyl, propyl,isobutyl, neo-pentyl, C₃-C₄ alkenyl or cyclopropyl-CH₂—, wherein theethyl, propyl, isobutyl, neo-pentyl, C₃-C₄ alkenyl and cyclopropylgroups may be optionally substituted with 1 to 3 fluoros or one methyland R₇ is methyl, ethyl, isopropyl, cyclopropyl or cyclobutyl, whereinthe methyl, ethyl, isopropyl, cyclopropyl and cyclobutyl may beoptionally substituted with one to three fluoro substituents or onemethyl; or a salt, enantiomer or N-oxide thereof.

One group of compounds according to this embodiment are compounds offormula (I-3a) which are compounds of formula (I-3) wherein X is O.

Another group of compounds according to this embodiment are compounds offormula (I-3b) which are compounds of formula (I-3) wherein X is S.

Compounds according to the invention may possess any number of benefitsincluding, inter alia, advantageous levels of biological activity forprotecting plants against diseases that are caused by fungi or superiorproperties for use as agrochemical active ingredients (for example,greater biological activity, an advantageous spectrum of activity, anincreased safety profile, improved physico-chemical properties, orincreased biodegradability).

Specific examples of compounds of formula (I) are illustrated in theTables A1 to A8 below: Table A1 provides 172 compounds of formula (I-c)

wherein R₁, R₂, R₃ and R₄ are all Hand wherein the values of R₅, R₆ and R₇ are as defined in Table Z-1below:

TABLE Z-1 Entry R₅ R₆ R₇ 1 CH₂CH(CH₃)₂ CH₃ CH₃ 2 CH₂C(CH₃)═CH₂ CH₃ CH₃ 3CH₂C(F)═CH₂ CH₃ CH₃ 4 CH₂C(CH₃)₃ CH₃ CH₃ 5 CH₂CF₃ CH₃ CH₃ 6 CH₂CH═CH₂CH₃ CH₃ 7 CH₂cyclopropyl CH₃ CH₃ 8 CH₂(1-methylcyclopropyl) CH₃ CH₃ 9CH₂(1-fluorocyclopropyl) CH₃ CH₃ 10 CH₂(1-cyanocyclopropyl) CH₃ CH₃ 11CH₂CF(CH₃)₂ CH₃ CH₃ 12 CH₂CF₂CH₃ CH₃ CH₃ 13 CH₂CH(CH₃)₂ CH₃ CH₂CH₃ 14CH₂C(CH₃)═CH₂ CH₃ CH₂CH₃ 15 CH₂C(F)═CH₂ CH₃ CH₂CH₃ 16 CH₂C(CH₃)₃ CH₃CH₂CH₃ 17 CH₂CF₃ CH₃ CH₂CH₃ 18 CH₂CH═CH₂ CH₃ CH₂CH₃ 19 CH₂cyclopropylCH₃ CH₂CH₃ 20 CH₂(1-methylcyclopropyl) CH₃ CH₂CH₃ 21CH₂(1-fluorocyclopropyl) CH₃ CH₂CH₃ 22 CH₂(1-cyanocyclopropyl) CH₃CH₂CH₃ 23 CH₂CF(CH₃)₂ CH₃ CH₂CH₃ 24 CH₂CF₂CH₃ CH₃ CH₂CH₃ 25 CH₂CH(CH₃)₂CH₃ CH(CH₃)₂ 26 CH₂C(CH₃)═CH₂ CH₃ CH(CH₃)₂ 27 CH₂C(F)═CH₂ CH₃ CH(CH₃)₂28 CH₂C(CH₃)₃ CH₃ CH(CH₃)₂ 29 CH₂CF₃ CH₃ CH(CH₃)₂ 30 CH₂CH═CH₂ CH₃CH(CH₃)₂ 31 CH₂cyclopropyl CH₃ CH(CH₃)₂ 32 CH₂(1-methylcyclopropyl) CH₃CH(CH₃)₂ 33 CH₂(1-fluorocyclopropyl) CH₃ CH(CH₃)₂ 34CH₂(1-cyanocyclopropyl) CH₃ CH(CH₃)₂ 35 CH₂CF(CH₃)₂ CH₃ CH(CH₃)₂ 36CH₂CF₂CH₃ CH₃ CH(CH₃)₂ 37 CH₂CH(CH₃)₂ CH₃ cyclopropyl 38 CH₂C(CH₃)═CH₂CH₃ cyclopropyl 39 CH₂C(F)═CH₂ CH₃ cyclopropyl 40 CH₂C(CH₃)₃ CH₃cyclopropyl 41 CH₂CF₃ CH₃ cyclopropyl 42 CH₂CH═CH₂ CH₃ cyclopropyl 43CH₂cyclopropyl CH₃ cyclopropyl 44 CH₂(1-methylcyclopropyl) CH₃cyclopropyl 45 CH₂(1-fluorocyclopropyl) CH₃ cyclopropyl 46CH₂(1-cyanocyclopropyl) CH₃ cyclopropyl 47 CH₂CF(CH₃)₂ CH₃ cyclopropyl48 CH₂CF₂CH₃ CH₃ cyclopropyl 49 CH₂CH(CH₃)₂ CH₃ C(CH₃)₃ 50 CH₂C(CH₃)═CH₂CH₃ C(CH₃)₃ 51 CH₂C(F)═CH₂ CH₃ C(CH₃)₃ 52 CH₂C(CH₃)₃ CH₃ C(CH₃)₃ 53CH₂CF₃ CH₃ C(CH₃)₃ 54 CH₂CH═CH₂ CH₃ C(CH₃)₃ 55 CH₂cyclopropyl CH₃C(CH₃)₃ 56 CH₂(1-methylcyclopropyl) CH₃ C(CH₃)₃ 57CH₂(1-fluorocyclopropyl) CH₃ C(CH₃)₃ 58 CH₂(1-cyanocyclopropyl) CH₃C(CH₃)₃ 59 CH₂CF(CH₃)₂ CH₃ C(CH₃)₃ 60 CH₂CF₂CH₃ CH₃ C(CH₃)₃ 61CH₂CH(CH₃)₂ CH₃ phenyl 62 CH₂C(CH₃)═CH₂ CH₃ phenyl 63 CH₂C(F)═CH₂ CH₃phenyl 64 CH₂C(CH₃)₃ CH₃ phenyl 65 CH₂CF₃ CH₃ phenyl 66 CH₂CH═CH₂ CH₃phenyl 67 CH₂cyclopropyl CH₃ phenyl 68 CH₂(1-methylcyclopropyl) CH₃phenyl 69 CH₂(1-fluorocyclopropyl) CH₃ phenyl 70 CH₂(1-cyanocyclopropyl)CH₃ phenyl 71 CH₂CF(CH₃)₂ CH₃ phenyl 72 CH₂CF₂CH₃ CH₃ phenyl 73CH₂CH(CH₃)₂ CH₃ CF(CH₃)₂ 74 CH₂C(CH₃)═CH₂ CH₃ CF(CH₃)₂ 75 CH₂C(F)═CH₂CH₃ CF(CH₃)₂ 76 CH₂C(CH₃)₃ CH₃ CF(CH₃)₂ 77 CH₂CF₃ CH₃ CF(CH₃)₂ 78CH₂CH═CH₂ CH₃ CF(CH₃)₂ 79 CH₂cyclopropyl CH₃ CF(CH₃)₂ 80CH₂(1-methylcyclopropyl) CH₃ CF(CH₃)₂ 81 CH₂(1-fluorocyclopropyl) CH₃CF(CH₃)₂ 82 CH₂(1-cyanocyclopropyl) CH₃ CF(CH₃)₂ 83 CH₂CF(CH₃)₂ CH₃CF(CH₃)₂ 84 CH₂CF₂CH₃ CH₃ CF(CH₃)₂ 85 CH₂CH(CH₃)₂ CH₃ Si(CH₃)₃ 86CH₂C(CH₃)═CH₂ CH₃ Si(CH₃)₃ 87 CH₂C(F)═CH₂ CH₃ Si(CH₃)₃ 88 CH₂C(CH₃)₃ CH₃Si(CH₃)₃ 89 CH₂CF₃ CH₃ Si(CH₃)₃ 90 CH₂CH═CH₂ CH₃ Si(CH₃)₃ 91CH₂cyclopropyl CH₃ Si(CH₃)₃ 92 CH₂(1-methylcyclopropyl) CH₃ Si(CH₃)₃ 93CH₂(1-fluorocyclopropyl) CH₃ Si(CH₃)₃ 94 CH₂(1-cyanocyclopropyl) CH₃Si(CH₃)₃ 95 CH₂CF(CH₃)₂ CH₃ Si(CH₃)₃ 96 CH₂CF₂CH₃ CH₃ Si(CH₃)₃ 97CH₂CH(CH₃)₂ CH₃ CF₃ 98 CH₂C(CH₃)═CH₂ CH₃ CF₃ 99 CH₂C(F)═CH₂ CH₃ CF₃ 100CH₂C(CH₃)₃ CH₃ CF₃ 101 CH₂CF₃ CH₃ CF₃ 102 CH₂CH═CH₂ CH₃ CF₃ 103CH₂cyclopropyl CH₃ CF₃ 104 CH₂(1-methylcyclopropyl) CH₃ CF₃ 105CH₂(1-fluorocyclopropyl) CH₃ CF₃ 106 CH₂(1-cyanocyclopropyl) CH₃ CF₃ 107CH₂CF(CH₃)₂ CH₃ CF₃ 108 CH₂CF₂CH₃ CH₃ CF₃ 109 CH₂CH(CH₃)₂ CH₃CH₂OCH(CH₃)₂ 110 CH₂C(CH₃)═CH₂ CH₃ CH₂OCH(CH₃)₂ 111 CH₂C(F)═CH₂ CH₃CH₂OCH(CH₃)₂ 112 CH₂C(CH₃)₃ CH₃ CH₂OCH(CH₃)₂ 113 CH₂CF₃ CH₃ CH₂OCH(CH₃)₂114 CH₂CH═CH₂ CH₃ CH₂OCH(CH₃)₂ 115 CH₂cyclopropyl CH₃ CH₂OCH(CH₃)₂ 116CH₂(1-methylcyclopropyl) CH₃ CH₂OCH(CH₃)₂ 117 CH₂(1-fluorocyclopropyl)CH₃ CH₂OCH(CH₃)₂ 118 CH₂(1-cyanocyclopropyl) CH₃ CH₂OCH(CH₃)₂ 119CH₂CF(CH₃)₂ CH₃ CH₂OCH(CH₃)₂ 120 CH₂CF₂CH₃ CH₃ CH₂OCH(CH₃)₂ 121CH₂CH(CH₃)₂ CH₃ 1-methylcycopropyl 122 CH₂C(CH₃)═CH₂ CH₃1-methylcycopropyl 123 CH₂C(F)═CH₂ CH₃ 1-methylcycopropyl 124 CH₂C(CH₃)₃CH₃ 1-methylcycopropyl 125 CH₂CF₃ CH₃ 1-methylcycopropyl 126 CH₂CH═CH₂CH₃ 1-methylcycopropyl 127 CH₂cyclopropyl CH₃ 1-methylcycopropyl 128CH₂(1-methylcyclopropyl) CH₃ 1-methylcycopropyl 129CH₂(1-fluorocyclopropyl) CH₃ 1-methylcycopropyl 130CH₂(1-cyanocyclopropyl) CH₃ 1-methylcycopropyl 131 CH₂CF(CH₃)₂ CH₃1-methylcycopropyl 132 CH₂CF₂CH₃ CH₃ 1-methylcycopropyl 133 CH₂CH(CH₃)₂CH₂OCH₃ CH₃ 134 CH₂C(CH₃)═CH₂ CH₂OCH₃ CH₃ 135 CH₂CF₃ CH₂OCH₃ CH₃ 136CH₂(1-methylcyclopropyl) CH₂OCH₃ CH₃ 137 CH₂(1-fluorocyclopropyl)CH₂OCH₃ CH₃ 138 CH₂CH(CH₃)₂ CH₂OCH₃ cyclopropyl 139 CH₂C(CH₃)═CH₂CH₂OCH₃ cyclopropyl 140 CH₂CF₃ CH₂OCH₃ cyclopropyl 141CH₂(1-methylcyclopropyl) CH₂OCH₃ cyclopropyl 142CH₂(1-fluorocyclopropyl) CH₂OCH₃ cyclopropyl 143 CH₂CH(CH₃)₂ CH₂OCH₃CH(CH₃)₂ 144 CH₂C(CH₃)═CH₂ CH₂OCH₃ CH(CH₃)₂ 145 CH₂CF₃ CH₂OCH₃ CH(CH₃)₂146 CH₂(1-methylcyclopropyl) CH₂OCH₃ CH(CH₃)₂ 147CH₂(1-fluorocyclopropyl) CH₂OCH₃ CH(CH₃)₂ 148 CH₂CH(CH₃)₂ CH₂OCH₃C(CH₃)₃ 149 CH₂C(CH₃)═CH₂ CH₂OCH₃ C(CH₃)₃ 150 CH₂CF₃ CH₂OCH₃ C(CH₃)₃ 151CH₂(1-methylcyclopropyl) CH₂OCH₃ C(CH₃)₃ 152 CH₂(1-fluorocyclopropyl)CH₂OCH₃ C(CH₃)₃ 153 CH₂CH(CH₃)₂ H CH₃ 154 CH₂C(CH₃)═CH₂ H CH₃ 155 CH₂CF₃H CH₃ 156 CH₂(1-methylcyclopropyl) H CH₃ 157 CH₂(1-fluorocyclopropyl) HCH₃ 158 CH₂CH(CH₃)₂ H cyclopropyl 159 CH₂C(CH₃)═CH₂ H cyclopropyl 160CH₂CF₃ H cyclopropyl 161 CH₂(1-methylcyclopropyl) H cyclopropyl 162CH₂(1-fluorocyclopropyl) H cyclopropyl 163 CH₂CH(CH₃)₂ H CH(CH₃)₂ 164CH₂C(CH₃)═CH₂ H CH(CH₃)₂ 165 CH₂CF₃ H CH(CH₃)₂ 166CH₂(1-methylcyclopropyl) H CH(CH₃)₂ 167 CH₂(1-fluorocyclopropyl) HCH(CH₃)₂ 168 CH₂CH(CH₃)₂ H C(CH₃)₃ 169 CH₂C(CH₃)═CH₂ H C(CH₃)₃ 170CH₂CF₃ H C(CH₃)₃ 171 CH₂(1-methylcyclopropyl) H C(CH₃)₃ 172CH₂(1-fluorocyclopropyl) H C(CH₃)₃Table A2 provides 172 compounds of formula (I-c) wherein R₁ is CH₃, R₂,R₃ and R₄ are all H and wherein the values of R₅, R₆ and R₇ are asdefined in Table Z-1 above.Table A3 provides 172 compounds of formula (I-c) wherein R₁ is F, R₂, R₃and R₄ are all H and wherein the values of R₅, R₆ and R₇ are as definedin Table Z-1 above.Table A4 provides 172 compounds of formula (I-c) wherein R₁ is CI, R₂,R₃ and R₄ are all H and wherein the values of R₅, R₆ and R₇ are asdefined in Table Z-1 above.Table A5 provides 172 compounds of formula (I-c) wherein R₁ and R₂ areF, R₃ and R₄ are H and wherein the values of R₅, R₆ and R₇ are asdefined in Table Z-1 above.Table A6 172 compounds of formula (I-c) wherein R₁ is F, R₂ is H, R₃ isCH₃ and R₄ is H and wherein the values of R₅, R₆ and R₇ are as definedin Table Z-1 above.Table A7 provides 172 compounds of formula (I-c) wherein R₁ is F, R₂ isH, R₃ is H and R₄ is CH₃ and wherein the values of R₅, R₆ and R₇ are asdefined in Table Z-1 above.Table A8 provides 172 compounds of formula (I-d)

wherein R₁ is F, R₂, R₃ and R₄ are all H and wherein the values of R₅,R₆ and R₇ are as defined in Table Z-1 above.

Additional specific examples of compounds of formula (I) are illustratedin the Tables B1 to B8 below:

Table B1 provides 128 compounds of formula (I-e)

wherein R₁, R₂, R₃ and R₄ are all Hand wherein the values of R₅, R₆ and R₇ are as defined in Table Z-2below:

TABLE Z-2 Entry R₅ R₆ R₇ 1 CH₂CH(CH₃)₂ H cyclopropyl 2 CH(CH₃)₂ Hcyclopropyl 3 CH₂CH₃ H cyclopropyl 4 C(CH₃)₃ H cyclopropyl 5 cyclopropylH cyclopropyl 6 CF₃ H cyclopropyl 7 CH₂CF₃ H cyclopropyl 8 CF(CH₃)₂ Hcyclopropyl 9 CH₃ CH₃ cyclopropyl 10 CH₂CH(CH₃)₂ CH₃ cyclopropyl 11CH(CH₃)₂ CH₃ cyclopropyl 12 CH₂CH₃ CH₃ cyclopropyl 13 cyclopropyl CH₃cyclopropyl 14 CF₃ CH₃ cyclopropyl 15 CH₂CF₃ CH₃ cyclopropyl 16 CF(CH₃)₂CH₃ cyclopropyl 17 CH₂CH(CH₃)₂ H phenyl 18 CH(CH₃)₂ H phenyl 19 CH₂CH₃ Hphenyl 20 C(CH₃)₃ H phenyl 21 cyclopropyl H phenyl 22 CF₃ H phenyl 23CH₂CF₃ H phenyl 24 CF(CH₃)₂ H phenyl 25 CH₃ CH₃ phenyl 26 CH₂CH(CH₃)₂CH₃ phenyl 27 CH(CH₃)₂ CH₃ phenyl 28 CH₂CH₃ CH₃ phenyl 29 cyclopropylCH₃ phenyl 30 CF₃ CH₃ phenyl 31 CH₂CF₃ CH₃ phenyl 32 CF(CH₃)₂ CH₃ phenyl33 CH₂CH(CH₃)₂ H 2-CH₃-phenyl 34 CH(CH₃)₂ H 2-CH₃-phenyl 35 CH₂CH₃ H2-CH₃-phenyl 36 C(CH₃)₃ H 2-CH₃-phenyl 37 cyclopropyl H 2-CH₃-phenyl 38CF₃ H 2-CH₃-phenyl 39 CH₂CF₃ H 2-CH₃-phenyl 40 CF(CH₃)₂ H 2-CH₃-phenyl41 CH₃ CH₃ 2-CH₃-phenyl 42 CH₂CH(CH₃)₂ CH₃ 2-CH₃-phenyl 43 CH(CH₃)₂ CH₃2-CH₃-phenyl 44 CH₂CH₃ CH₃ 2-CH₃-phenyl 45 cyclopropyl CH₃ 2-CH₃-phenyl46 CF₃ CH₃ 2-CH₃-phenyl 47 CH₂CF₃ CH₃ 2-CH₃-phenyl 48 CF(CH₃)₂ CH₃2-CH₃-phenyl 49 CH₂CH(CH₃)₂ H 2-F-phenyl 50 CH(CH₃)₂ H 2-F-phenyl 51CH₂CH₃ H 2-F-phenyl 52 C(CH₃)₃ H 2-F-phenyl 53 cyclopropyl H 2-F-phenyl54 CF₃ H 2-F-phenyl 55 CH₂CF₃ H 2-F-phenyl 56 CF(CH₃)₂ H 2-F-phenyl 57CH₃ CH₃ 2-F-phenyl 58 CH₂CH(CH₃)₂ CH₃ 2-F-phenyl 59 CH(CH₃)₂ CH₃2-F-phenyl 60 CH₂CH₃ CH₃ 2-F-phenyl 61 cyclopropyl CH₃ 2-F-phenyl 62 CF₃CH₃ 2-F-phenyl 63 CH₂CF₃ CH₃ 2-F-phenyl 64 CF(CH₃)₂ CH₃ 2-F-phenyl 65CH₂CH(CH₃)₂ H 2-Cl-phenyl 66 CH(CH₃)₂ H 2-Cl-phenyl 67 CH₂CH₃ H2-Cl-phenyl 68 C(CH₃)₃ H 2-Cl-phenyl 69 cyclopropyl H 2-Cl-phenyl 70 CF₃H 2-Cl-phenyl 71 CH₂CF₃ H 2-Cl-phenyl 72 CF(CH₃)₂ H 2-Cl-phenyl 73 CH₃CH₃ 2-Cl-phenyl 74 CH₂CH(CH₃)₂ CH₃ 2-Cl-phenyl 75 CH(CH₃)₂ CH₃2-Cl-phenyl 76 CH₂CH₃ CH₃ 2-Cl-phenyl 77 cyclopropyl CH₃ 2-Cl-phenyl 78CF₃ CH₃ 2-Cl-phenyl 79 CH₂CF₃ CH₃ 2-Cl-phenyl 80 CF(CH₃)₂ CH₃2-Cl-phenyl 81 CH₂CH(CH₃)₂ H 2-OCH₃-phenyl 82 CH(CH₃)₂ H 2-OCH₃-phenyl83 CH₂CH₃ H 2-OCH₃-phenyl 84 C(CH₃)₃ H 2-OCH₃-phenyl 85 cyclopropyl H2-OCH₃-phenyl 86 CF₃ H 2-OCH₃-phenyl 87 CH₂CF₃ H 2-OCH₃-phenyl 88CF(CH₃)₂ H 2-OCH₃-phenyl 89 CH₃ CH₃ 2-OCH₃-phenyl 90 CH₂CH(CH₃)₂ CH₃2-OCH₃-phenyl 91 CH(CH₃)₂ CH₃ 2-OCH₃-phenyl 92 CH₂CH₃ CH₃ 2-OCH₃-phenyl93 cyclopropyl CH₃ 2-OCH₃-phenyl 94 CF₃ CH₃ 2-OCH₃-phenyl 95 CH₂CF₃ CH₃2-OCH₃-phenyl 96 CF(CH₃)₂ CH₃ 2-OCH₃-phenyl 97 CH₃ CH₂CH₃ phenyl 98CH₂CH(CH₃)₂ CH₂CH₃ phenyl 99 CH(CH₃)₂ CH₂CH₃ phenyl 100 CH₂CH₃ CH₂CH₃phenyl 101 cyclopropyl CH₂CH₃ phenyl 102 CF₃ CH₂CH₃ phenyl 103 CH₂CF₃CH₂CH₃ phenyl 104 CF(CH₃)₂ CH₂CH₃ phenyl 105 CH₃ CH₃ 3-CH₃-phenyl 106CH₂CH(CH₃)₂ CH₃ 3-CH₃-phenyl 107 CH(CH₃)₂ CH₃ 3-CH₃-phenyl 108 CH₂CH₃CH₃ 3-CH₃-phenyl 109 CH₃ CH₃ 3-F-phenyl 110 CH₂CH(CH₃)₂ CH₃ 3-F-phenyl111 CH(CH₃)₂ CH₃ 3-F-phenyl 112 CH₂CH₃ CH₃ 3-F-phenyl 113 CH₃ CH₃3-OCH₃-phenyl 114 CH₂CH(CH₃)₂ CH₃ 3-OCH₃-phenyl 115 CH(CH₃)₂ CH₃3-OCH₃-phenyl 116 CH₂CH₃ CH₃ 3-OCH₃-phenyl 117 CH₃ CH₃ 4-CH₃-phenyl 118CH₂CH(CH₃)₂ CH₃ 4-CH₃-phenyl 119 CH(CH₃)₂ CH₃ 4-CH₃-phenyl 120 CH₂CH₃CH₃ 4-CH₃-phenyl 121 CH₃ CH₃ 4-OCH₃-phenyl 122 CH₂CH(CH₃)₂ CH₃4-OCH₃-phenyl 123 CH(CH₃)₂ CH₃ 4-OCH₃-phenyl 124 CH₂CH₃ CH₃4-OCH₃-phenyl 125 CH₃ CH₃ 4-F-phenyl 126 CH₂CH(CH₃)₂ CH₃ 4-F-phenyl 127CH(CH₃)₂ CH₃ 4-F-phenyl 128 CH₂CH₃ CH₃ 4-F-phenylTable B2 provides 128 compounds of formula (I-e) wherein R₁ is CH₃, R₂,R₃ and R₄ are all H and wherein the values of R₅, R₆ and R₇ are asdefined in Table Z-2 above.Table B3 provides 128 compounds of formula (I-e) wherein R₁ is F, R₂, R₃and R₄ are all H and wherein the values of R₅, R₆ and R₇ are as definedin Table Z-2 above.Table B4 provides 128 compounds of formula (I-e) wherein R₁ is CI, R₂,R₃ and R₄ are all H and wherein the values of R₅, R₆ and R₇ are asdefined in Table Z-2 above.Table B5 provides 128 compounds of formula (I-e) wherein R₁ and R₂ areF, R₃ and R₄ are H and wherein the values of R₅, R₆ and R₇ are asdefined in Table Z-2 above.Table B6 provides 128 compounds of formula (I-e) wherein R₁ is F, R₂ isH, R₃ is CH₃ and R₄ is H and wherein the values of R₅, R₆ and R₇ are asdefined in Table Z-2 above.Table B7 provides 128 compounds of formula (I-e) wherein R₁ is F, R₂ isH, R₃ is H and R₄ is CH₃ and wherein the values of R₅, R₆ and R₇ are asdefined in Table Z-2 above.Table B8 provides 128 compounds of formula (I-f)

wherein R₁ is F, R₂, R₃ and R₄ are all H and wherein the values of R₅,R₆ and R₇ are as defined in Table Z-2 above.

Compounds of the present invention can be made as shown in the followingschemes, in which, unless otherwise stated, the definition of eachvariable is as defined above for a compound of formula (I).

A shown in scheme 1, compounds of general formula (I-a) wherein X is Oand wherein R₁, R₂, R₃, R₄, R₅, R₆, R₇ and A are as defined forcompounds of formula (I), can be prepared by the reaction of compoundsof formula (II) with amines of formula (III).

Among the various reported methods for this transformation, the mostwidely applied involve treatment of carboxylic acid (II) with anactivating agent like thionyl chloride or an amide coupling reagent likedicyclohexylcarbodiimide in an inert organic solvent liketetrahydrofuran (THF) or dimethylformamide (DMF) and reaction with amine(III) in the presence of a catalyst like dimethylaminopyridine asdescribed in Chem. Soc. Rev., 2009, 606-631 or Tetrahedron 2005,10827-10852.

Alternatively, compounds of general formula (I-a) wherein X is O andwherein R₁, R₂, R₃, R₄, R₅, R₆, R₇ and A are as defined for compounds offormula (I), can also be prepared by the reaction of compounds offormula (IV) with amines of formula (III), carbon monoxide, a base liketriethylamine or potassium carbonate and a suitably supportedtransitional metal catalyst like palladium in an inert organic solventlike 1,4-dioxane at a temperature between 20° C. and 110° C. asdescribed in Org. Lett., 2014, 4296-4299 (and references therein) andshown in scheme 2.

Alternatively, compounds of general formula (I-a) wherein X is O andwherein R₁, R₂, R₃, R₄, R₅, R₆, R₇ and A are as defined for compounds offormula (I), can also be prepared by the reaction of organometalliccompounds of formula (IVa) with isocyanates of formula (IIIa) in aninert organic solvent like diethyl ether or THF at temperatures between−78° C. and +40° C. as described in Angew. Chem. Int. Ed. 2012,9173-9175 and shown in scheme 3.

The preparation of organometallic compounds of formula (IVa) fromcompounds of formula (IV) by lithium-halogen exchange with an alkyllithium reagent like s-butyl lithium, direct zinc insertion ormagnesium-halogen exchange with tri n-butyl magnesate is known to aperson skilled in the art, and is described in synthetic chemistry textssuch as March's Advanced Organic Chemistry.

As shown in scheme 4, compounds of formula (III) and (IIIa) can beprepared from carboxylic acid derivatives of formula (Va) or (Vb)through an intermediary isocyanate of formula (IIIa) or a carbamate offormula (IIIb), where R₁₄ is C₁-C₄ alkyl, is which can be hydrolyzedwith aqueous acid or base at temperatures between 0° C. and 100° C. asshown in scheme 4.

Among the various protocols reported for the transformation ofcarboxylic acid derivatives (Va) or (Vb) to isocyanate (IIIa), thefollowing have found wide spread application:

1) Treatment of acid (Va) with diphenylphosphoryl azide and an aminebase like tributylamine in an inert organic solvent like toluene attemperatures between 50° C. and 120° C. to give isocyanate (IIIa) asdescribed in Aust. J. Chem., 1973, 1591-3.

2) Treatment of acid (Va) with an activating agent like thionyl chlorideor propylphosphonic anhydride in the presence of an azide source likesodium azide and an amine base like triethyl amine in an inert solventlike THF at temperatures between 20° C. and 100° C., followed by thermalrearrangement in an inert solven such as toluene as described inSynthesis 2011, 1477-1483.

3) Conversion of acid (Va) to the corresponding hydroxamic acids whichcan then be treated with a dehydrating agent like para-toluenesulfonylchloride and a base like triethylamine in an inert organic solvent liketoluene at temperatures between 20° C. and 120° C.

4) Conversion of acid (Va) to the corresponding primary carboxamide (Vb)which can then be treated with an oxidizing agent such asdiacetoxyiodobenzene and an acid such as trifluoroacetic acid orpara-toluenesulfonic acid in a solvent like acetonitrile at temperaturesbetween 0° C. and 100° C. as described in J. Org. Chem. 1984, 4212-4216.Alternatively primary carboxamide (Vb) can then be treated with anoxidizing agent such as bromine and a base such as sodium hydroxide in asolvent like water or methanol at temperatures between 0° C. and 100° C.

A person skilled in the art will appreciate that carboxylic acids offormula (Va) and amide (Vb) can be prepared from the correspondingesters. Similarly a person skilled in the art will appreciate that thealpha position of these esters can be functionalized by deprotonationwith a strong base like lithium diisopropylamide in an inert solventlike THF at temperatures between −78° C. and 20° C. followed by reactionwith an electrophilic reagent such as an alkyl halide as described inMarch's Advanced Organic Chemistry, Smith and March, 6^(th) edition,Wiley, 2007. This reaction can be repeated and the introduced alkyl,alkenyl and alkynyl groups can be further functionalized byhalogenation, cyclopropanation, oxidation or reduction, cross coupling(e.g. Sonogashira coupling) to prepare acid derivatives of formula (Va)and (Vb) from commercially available esters.

Amines of formula (III) wherein A is a direct bond are commerciallyavailable or can be prepared in multistep sequences using transformationthat belongs to the knowledge of a person skilled in the art. Examplesof amine preparation can be found in EP943602 or in J. Org. Chem. 2014,79, 1254-1264. As shown in scheme 5, amines of formula (III) wherein Ais a direct bond can be prepared also from compounds of formula (IIIc)by condensation with a sulfinamide (IIIe), where R₉ is C₂-C₆alkyl orphenyl and the phenyl group can be substituted with 1 to 3 groupsindependently selected from C₁-C₄alkyl and nitro, in the presence of adehydrating agent like Ti(OEt)₄ to form sulfimines of formula (IIIf)which can then be treated with an organometallic reagent of formula(IIIg), where Y is lithium, a copper, an aluminum- or a magnesium-salt,in an inert solvent like THF at temperatures between −78° C. and +70°C., followed by an acidic hydrolysis of the sulfonamide; a sequencegenerally known to a person skilled in the art and also described inChem. Rev. 2010, 3600-3740.

Alternatively, amines of formula (IIIi) where A is —CH₂— can be alsoprepared by the sequences shown in scheme 6:

-   -   1) Reduction of amino acids of formula (VIb) with a reducing        agent such as LiAlH₄ in an inert solvent like THF to form amino        alcohols of formula (VIa), followed by sulfonylation, ring        closure to an aziridine of formula (VI), ring opening of the        aziridine with organometallic reagents like (IIIg) (as described        for instance in Synlett, 2004, 10, 1691-1694) and removal of the        sulfonyl group    -   2) Aziridination of olefins of formula (VIc) to form aziridines        of formula (VI) with sulfonamides, an oxidizing agent and a        rhodium catalyst as described in Org. Lett., 2005, 2787-2790,        followed by ring opening of the aziridine with (IIIg) and        removal of the sulfonyl group as described in the section above.

A large selection of amino acids of formula (VIb) and olefins of formula(VIc) are commercially available and general protocols for theirpreparation has been reported in the chemical literature and are knownto a person skilled in the art.

As shown in scheme 8, compounds of general formula (I-b) wherein X is Scan be prepared from compounds of general formula (I-a) wherein X is Oby treatment with a deoxothionating agent like P₄S₁₀ or Lawesson reagentin an inert organic solvent like toluene at temperatures between 20° C.and 150° C.

As shown in scheme 9, carboxylic acids of formula (II) wherein X is Oand wherein R₁, R₂, R₃ and R₄ are as defined for compounds of formula(I), can be prepared by various methods and many are commerciallyavailable. Among the many reported methods for their preparation, thefollowing have been widely applied:

1) Transformation of anilines of formula (VII) to quinolones of formula(VIIb) by reaction with a malonate derivative of formula (Vila) in aninert solvent like diphenyl ether at temperatures between 100° C. and260° C. as described in US 20070015758, followed by well-knownfunctional group interconversion which is generally known to a personskilled in the art and also described in WO 2007133637.

2) Transformation of compounds of formula (IV) to organometallicintermediates (IVa) by lithium-halogen exchange with an alkyl lithiumreagent like s-butyl lithium or magnesium-halogen exchange with trin-butyl magnesate in an ethereal solvent like THF at temperaturesbetween −90° C. and +20° C. and subsequent reaction with CO₂.

3) Transformation of compounds of formula (IV) in the presence of acarbon monoxide source, a base like triethylamine, water or anequivalent thereof and a suitably ligated transition metal catalystcontaining for example palladium as described in J. Am. Chem. Soc. 2013,2891-2894 (and references therein) or Tetrahedron 2003, 8629-8640.

As shown in scheme 10, compounds of formula (IV) can be prepared bytreatment of compounds of formula (IVf) with a halogenating agent likeN-iodosuccinimide, bromine or chlorine in an inert solvent as describedin WO 2005113539 or JP 2001322979. Alternatively, compounds of formula(IV) can be prepared by treatment of propargylated anilines of formula(IVg) with a halogenating agent like iodine in an inert solvent likeacetonitrile and a base like sodium hydrogen carbonate at temperaturesbetween 0° C. and 80° C. as described in Org. Lett. 2005, 763-766.

The preparation of propargylated anilines of formula (IVh) from thecorresponding commercially available anilines is trivial to a personskilled in the art and described in March's Advanced Organic Chemistry,Smith and March, 6^(th) edition, Wiley, 2007.

The synthesis of compounds of formula (IVf) is generally known to aperson skilled in the art and a large selection of compounds iscommercially available.

Alternatively, the compounds of formula (I-a) wherein R₁, R₂, R₃, R₄,R₅, R₆ and R₇ are as defined for compounds of formula (I) and X is O,can be obtained by transformation of another, closely related, compoundof formula (I-a) using standard synthesis techniques known to the personskilled in the art. Non-exhaustive examples include oxidation reactions,reduction reactions, hydrolysis reactions, coupling reactions, aromaticnucleophilic or electrophilic substitution reactions, nucleophilicsubstitution reactions, nucleophilic addition reactions, cycloadditionreactions and halogenation reactions.

Certain intermediates described in the above schemes are novel and assuch form a further aspect of the invention.

The compounds of formula (I) can be used in the agricultural sector andrelated fields of use e.g. as active ingredients for controlling plantpests or on non-living materials for control of spoilage microorganismsor organisms potentially harmful to man. The novel compounds aredistinguished by excellent activity at low rates of application, bybeing well tolerated by plants and by being environmentally safe. Theyhave very useful curative, preventive and systemic properties and may beused for protecting numerous cultivated plants. The compounds of formula(I) can be used to inhibit or destroy the pests that occur on plants orparts of plants (fruit, blossoms, leaves, stems, tubers, roots) ofdifferent crops of useful plants, while at the same time protecting alsothose parts of the plants that grow later e.g. from phytopathogenicmicroorganisms.

It is also possible to use compounds of formula (I) as fungicide. Theterm “fungicide” as used herein means a compound that controls,modifies, or prevents the growth of fungi. The term “fungicidallyeffective amount” means the quantity of such a compound or combinationof such compounds that is capable of producing an effect on the growthof fungi. Controlling or modifying effects include all deviation fromnatural development, such as killing, retardation and the like, andprevention includes barrier or other defensive formation in or on aplant to prevent fungal infection.

It is also possible to use compounds of formula (I) as dressing agentsfor the treatment of plant propagation material, e.g., seed, such asfruits, tubers or grains, or plant cuttings (for example rice), for theprotection against fungal infections as well as against phytopathogenicfungi occurring in the soil. The propagation material can be treatedwith a composition comprising a compound of formula (I) before planting:seed, for example, can be dressed before being sown. The compounds offormula (I) can also be applied to grains (coating), either byimpregnating the seeds in a liquid formulation or by coating them with asolid formulation. The composition can also be applied to the plantingsite when the propagation material is being planted, for example, to theseed furrow during sowing. The invention relates also to such methods oftreating plant propagation material and to the plant propagationmaterial so treated.

Furthermore the compounds according to present invention can be used forcontrolling fungi in related areas, for example in the protection oftechnical materials, including wood and wood related technical products,in food storage, in hygiene management.

In addition, the invention could be used to protect non-living materialsfrom fungal attack, e.g. lumber, wall boards and paint.

Compounds of formula (I) and fungicidal compositions containing them maybe used to control plant diseases caused by a broad spectrum of fungalplant pathogens. They are effective in controlling a broad spectrum ofplant diseases, such as foliar pathogens of ornamental, turf, vegetable,field, cereal, and fruit crops.

These fungi and fungal vectors of disease, as well as phytopathogenicbacteria and viruses, which may be controlled are for example:

Absidia corymbifera, Alternaria spp, Aphanomyces spp, Ascochyta spp,Aspergillus spp. including A. flavus, A. fumigatus, A. nidulans, A.niger, A. terrus, Aureobasidium spp. including A. pullulans, Blastomycesdermatitidis, Blumeria graminis, Bremia lactucae, Botryosphaeria spp.including B. dothidea, B. obtusa, Botrytis spp. inclusing B. cinerea,Candida spp. including C. albicans, C. glabrata, C. krusei, C.lusitaniae, C. parapsilosis, C. tropicalis, Cephaloascus fragrans,Ceratocystis spp, Cercospora spp. including C. arachidicola,Cercosporidium personatum, Cladosporium spp, Claviceps purpurea,

Coccidioides immitis, Cochliobolus spp, Colletotrichum spp. including C.musae,

Cryptococcus neoformans, Diaporthe spp, Didymella spp, Drechslera spp,Elsinoe spp,

Epidermophyton spp, Erwinia amylovora, Erysiphe spp. including E.cichoracearum,

Eutypa lata, Fusarium spp. including F. culmorum, F. graminearum, F.langsethiae, F. moniliforme, F. oxysporum, F. proliferatum, F.subglutinans, F. solani, Gaeumannomyces graminis, Gibberella fujikuroi,Gloeodes pomigena, Gloeosporium musarum, Glomerella cingulate,Guignardia bidwellii, Gymnosporangium juniperi-virginianae,Helminthosporium spp, Hemileia spp, Histoplasma spp. including H.capsulatum, Laetisaria fuciformis, Leptographium lindbergi, Leveillulataurica, Lophodermium seditiosum, Microdochium nivale, Microsporum spp,Monilinia spp, Mucor spp, Mycosphaerella spp. including M. graminicola,M. pomi, Oncobasidium theobromaeon, Ophiostoma piceae, Paracoccidioidesspp, Penicillium spp. including P. digitatum, P. italicum, Petriellidiumspp, Peronosclerospora spp. Including P. maydis, P. philippinensis andP. sorghi, Peronospora spp, Phaeosphaeria nodorum, Phakopsorapachyrhizi, Phellinus igniarus, Phialophora spp, Phoma spp, Phomopsisviticola, Phytophthora spp. including P. infestans, Plasmopara spp.including P. halstedii, P. viticola, Pleospora spp., Podosphaera spp.including P. leucotricha, Polymyxa graminis, Polymyxa betae,Pseudocercosporella herpotrichoides, Pseudomonas spp, Pseudoperonosporaspp. including P. cubensis, P. humuli, Pseudopeziza tracheiphila,Puccinia Spp. including P. hordei, P. recondita, P. striiformis, P.triticina, Pyrenopeziza spp, Pyrenophora spp, Pyricularia spp. includingP. oryzae, Pythium spp. including P. ultimum, Ramularia spp, Rhizoctoniaspp, Rhizomucor pusillus, Rhizopus arrhizus, Rhynchosporium spp,Scedosporium spp. including S. apiospermum and S. prolificans,Schizothyrium pomi,

Sclerotinia spp, Sclerotium spp, Septoria spp, including S. nodorum, S.tritici, Sphaerotheca macularis, Sphaerotheca fusca (Sphaerothecafuliginea), Sporothorix spp, Stagonospora nodorum, Stemphylium spp,Stereum hirsutum, Thanatephorus cucumeris, Thielaviopsis basicola,Tilletia spp, Trichoderma spp. including T. harzianum, T.pseudokoningii, T. viride,

Trichophyton spp, Typhula spp, Uncinula necator, Urocystis spp, Ustilagospp, Venturia spp. including V. inaequalis, Verticillium spp, andXanthomonas spp.

In particular, compounds of formula (I) and fungicidal compositionscontaining them may be used to control plant diseases caused by a broadspectrum of fungal plant pathogens in the Basidiomycete, Ascomycete,Oomycete and/or Deuteromycete, Blasocladiomycete, Chrytidiomycete,Glomeromycete and/or Mucoromycete classes.

These pathogens may include:

Oomycetes, including Phytophthora diseases such as those caused byPhytophthora capsici, Phytophthora infestans, Phytophthora sojae,Phytophthora fragariae, Phytophthora nicotianae, Phytophthora cinnamomi,Phytophthora citricola, Phytophthora citrophthora and Phytophthoraerythroseptica; Pythium diseases such as those caused by Pythiumaphanidermatum, Pythium arrhenomanes, Pythium graminicola, Pythiumirregulare and Pythium ultimum; diseases caused by Peronosporales suchas Peronospora destructor, Peronospora parasitica, Plasmopara viticola,Plasmopara halstedii, Pseudoperonospora cubensis, Albugo candida,Sclerophthora macrospora and Bremia lactucae; and others such asAphanomyces cochlioides, Labyrinthula zosterae, Peronosclerospora sorghiand Sclerospora graminicola.

Ascomycetes, including blotch, spot, blast or blight diseases and/orrots for example those caused by Pleosporales such as Stemphyliumsolani, Stagonospora tainanensis, Spilocaea oleaginea, Setosphaeriaturcica, Pyrenochaeta lycoperisici, Pleospora herbarum, Phomadestructiva, Phaeosphaeria herpotrichoides, Phaeocryptocus gaeumannii,Ophiosphaerella graminicola, Ophiobolus graminis, Leptosphaeriamaculans, Hendersonia creberrima, Helminthosporium triticirepentis,Setosphaeria turcica, Drechslera glycines, Didymella bryoniae,Cycloconium oleagineum, Corynespora cassiicola, Cochliobolus sativus,Bipolaris cactivora, Venturia inaequalis, Pyrenophora teres, Pyrenophoratritici-repentis, Alternaria alternata, Alternaria brassicicola,Alternaria solani and Alternaria tomatophila, Capnodiales such asSeptoria tritici, Septoria nodorum, Septoria glycines, Cercosporaarachidicola, Cercospora sojina, Cercospora zeae-maydis, Cercosporellacapsellae and Cercosporella herpotrichoides, Cladosporium carpophilum,Cladosporium effusum, Passalora fulva, Cladosporium oxysporum,Dothistroma septosporum, Isariopsis clavispora, Mycosphaerellafijiensis, Mycosphaerella graminicola, Mycovellosiella koepkeii,Phaeoisariopsis bataticola, Pseudocercospora vitis, Pseudocercosporellaherpotrichoides, Ramularia beticola, Ramularia collo-cygni,Magnaporthales such as Gaeumannomyces graminis, Magnaporthe grisea,Pyricularia oryzae, Diaporthales such as Anisogramma anomala,Apiognomonia errabunda, Cytospora platani, Diaporthe phaseolorum,Discula destructiva, Gnomonia fructicola, Greeneria uvicola, Melanconiumjuglandinum, Phomopsis viticola, Sirococcusclavigignenti-juglandacearum, Tubakia dryina, Dicarpella spp., Valsaceratosperma, and others such as Actinothyrium graminis, Ascochyta pisi,Aspergillus flavus, Aspergillus fumigatus, Aspergillus nidulans,Asperisporium caricae, Blumeriella jaapii, Candida spp., Capnodiumramosum, Cephaloascus spp., Cephalosporium gramineum, Ceratocystisparadoxa, Chaetomium spp., Hymenoscyphus pseudoalbidus, Coccidioidesspp., Cylindrosporium padi, Diplocarpon malae, Drepanopeziza campestris,Elsinoe ampelina, Epicoccum nigrum, Epidermophyton spp., Eutypa lata,Geotrichum candidum, Gibellina cerealis, Gloeocercospora sorghi,Gloeodes pomigena, Gloeosporium perennans; Gloeotinia temulenta,Griphospaeria corticola, Kabatiella lini, Leptographium microsporum,Leptosphaerulinia crassiasca, Lophodermium seditiosum, Marssoninagraminicola, Microdochium nivale, Monilinia fructicola, Monographellaalbescens, Monosporascus cannonballus, Naemacyclus spp., Ophiostomanovo-ulmi, Paracoccidioides brasiliensis, Penicillium expansum,Pestalotia rhododendri, Petrieffidium spp., Pezicula spp., Phialophoragregata, Phyllachora pomigena, Phymatotrichum omnivora, Physalosporaabdita, Plectosporium tabacinum, Polyscytalum pustulans, Pseudopezizamedicaginis, Pyrenopeziza brassicae, Ramulispora sorghi, Rhabdoclinepseudotsugae, Rhynchosporium secalis, Sacrocladium oryzae, Scedosporiumspp., Schizothyrium pomi, Sclerotinia sclerotiorum, Sclerotinia minor;Sclerotium spp., Typhula ishikariensis, Seimatosporium mariae,Lepteutypa cupressi, Septocyta ruborum, Sphaceloma perseae, Sporonemaphacidioides, Stigmina palmivora, Tapesia yallundae, Taphrina bullata,Thielviopsis basicola, Trichoseptoria fructigena, Zygophialajamaicensis; powdery mildew diseases for example those caused byErysiphales such as Blumeria graminis, Erysiphe polygoni, Uncinulanecator, Sphaerotheca fuligena, Podosphaera leucotricha, Podospaeramacularis Golovinomyces cichoracearum, Leveillula taurica, Microsphaeradiffusa, Oidiopsis gossypii, Phyllactinia guttata and Oidium arachidis;molds for example those caused by Botryosphaeriales such as Dothiorellaaromatica, Diplodia seriata, Guignardia bidwellii, Botrytis cinerea,Botryotinia allii, Botryotinia fabae, Fusicoccum amygdali, Lasiodiplodiatheobromae, Macrophoma theicola, Macrophomina phaseolina, Phyllostictacucurbitacearum; anthracnoses for example those caused by Glommerelalessuch as Colletotrichum gloeosporioides, Colletotrichum lagenarium,Colletotrichum gossypii, Glomerella cingulata, and Colletotrichumgraminicola; and wilts or blights for example those caused byHypocreales such as Acremonium strictum, Claviceps purpurea, Fusariumculmorum, Fusarium graminearum, Fusarium virguliforme, Fusariumoxysporum, Fusarium subglutinans, Fusarium oxysporum f.sp. cubense,Gerlachia nivale, Gibberella fujikuroi, Gibberella zeae, Gliocladiumspp., Myrothecium verrucaria, Nectria ramulariae, Trichoderma viride,Trichothecium roseum, and Verticillium theobromae.

Basidiomycetes, including smuts for example those caused byUstilaginales such as Ustilaginoidea virens, Ustilago nuda, Ustilagotritici, Ustilago zeae, rusts for example those caused by Puccinialessuch as Cerotelium fici, Chrysomyxa arctostaphyli, Coleosporiumipomoeae, Hemileia vastatrix, Puccinia arachidis, Puccinia cacabata,Puccinia graminis, Puccinia recondita, Puccinia sorghi, Puccinia hordei,Puccinia striiformis f.sp. Hordei, Puccinia striiformis f.sp. Secalis,Pucciniastrum coryli, or Uredinales such as Cronartium ribicola,Gymnosporangium juniperi-viginianae, Melampsora medusae, Phakopsorapachyrhizi, Phragmidium mucronatum, Physopella ampelosidis, Tranzscheliadiscolor and Uromyces viciae-fabae; and other rots and diseases such asthose caused by Cryptococcus spp., Exobasidium vexans, Marasmiellusinoderma, Mycena spp., Sphacelotheca reiliana, Typhula ishikariensis,Urocystis agropyri, Itersonilia perplexans, Corticium invisum,Laetisaria fuciformis, Waitea circinata, Rhizoctonia solani,Thanetephorus cucurmeris, Entyloma dahliae, Entylomella microspora,Neovossia moliniae and Tilletia caries.

Blastocladiomycetes, such as Physoderma maydis.

Mucoromycetes, such as Choanephora cucurbitarum; Mucor spp.; Rhizopusarrhizus,

As well as diseases caused by other species and genera closely relatedto those listed above.

In addition to their fungicidal activity, the compounds and compositionscomprising them may also have activity against bacteria such as Erwiniaamylovora, Erwinia caratovora, Xanthomonas campestris, Pseudomonassyringae, Strptomyces scabies and other related species as well ascertain protozoa.

Within the scope of present invention, target crops and/or useful plantsto be protected typically comprise perennial and annual crops, such asberry plants for example blackberries, blueberries, cranberries,raspberries and strawberries; cereals for example barley, maize (corn),millet, oats, rice, rye, sorghum triticale and wheat; fibre plants forexample cotton, flax, hemp, jute and sisal; field crops for examplesugar and fodder beet, coffee, hops, mustard, oilseed rape (canola),poppy, sugar cane, sunflower, tea and tobacco; fruit trees for exampleapple, apricot, avocado, banana, cherry, citrus, nectarine, peach, pearand plum; grasses for example Bermuda grass, bluegrass, bentgrass,centipede grass, fescue, ryegrass, St. Augustine grass and Zoysia grass;herbs such as basil, borage, chives, coriander, lavender, lovage, mint,oregano, parsley, rosemary, sage and thyme; legumes for example beans,lentils, peas and soya beans; nuts for example almond, cashew, groundnut, hazelnut, peanut, pecan, pistachio and walnut; palms for exampleoil palm; ornamentals for example flowers, shrubs and trees; othertrees, for example cacao, coconut, olive and rubber; vegetables forexample asparagus, aubergine, broccoli, cabbage, carrot, cucumber,garlic, lettuce, marrow, melon, okra, onion, pepper, potato, pumpkin,rhubarb, spinach and tomato; and vines for example grapes.

The useful plants and/or target crops in accordance with the inventioninclude conventional as well as genetically enhanced or engineeredvarieties such as, for example, insect resistant (e.g. Bt. and VIPvarieties) as well as disease resistant, herbicide tolerant (e.g.glyphosate- and glufosinate-resistant maize varieties commerciallyavailable under the trade names RoundupReady® and LibertyLink®) andnematode tolerant varieties. By way of example, suitable geneticallyenhanced or engineered crop varieties include the Stoneville 5599BRcotton and Stoneville 4892BR cotton varieties.

The term “useful plants” and/or “target crops” is to be understood asincluding also useful plants that have been rendered tolerant toherbicides like bromoxynil or classes of herbicides (such as, forexample, HPPD inhibitors, ALS inhibitors, for example primisulfuron,prosulfuron and trifloxysulfuron, EPSPS(5-enol-pyrovyl-shikimate-3-phosphate-synthase) inhibitors, GS(glutamine synthetase) inhibitors or PPO (protoporphyrinogen-oxidase)inhibitors) as a result of conventional methods of breeding or geneticengineering. An example of a crop that has been rendered tolerant toimidazolinones, e.g. imazamox, by conventional methods of breeding(mutagenesis) is Clearfield® summer rape (Canola). Examples of cropsthat have been rendered tolerant to herbicides or classes of herbicidesby genetic engineering methods include glyphosate- andglufosinate-resistant maize varieties commercially available under thetrade names RoundupReady®, Herculex I® and LibertyLink®.

The term “useful plants” and/or “target crops” is to be understood asincluding those which naturally are or have been rendered resistant toharmful insects. This includes plants transformed by the use ofrecombinant DNA techniques, for example, to be capable of synthesisingone or more selectively acting toxins, such as are known, for example,from toxin-producing bacteria. Examples of toxins which can be expressedinclude δ-endotoxins, vegetative insecticidal proteins (Vip),insecticidal proteins of bacteria colonising nematodes, and toxinsproduced by scorpions, arachnids, wasps and fungi. An example of a cropthat has been modified to express the Bacillus thuringiensis toxin isthe Bt maize KnockOut® (Syngenta Seeds). An example of a crop comprisingmore than one gene that codes for insecticidal resistance and thusexpresses more than one toxin is VipCot® (Syngenta Seeds). Crops or seedmaterial thereof can also be resistant to multiple types of pests(so-called stacked transgenic events when created by geneticmodification). For example, a plant can have the ability to express aninsecticidal protein while at the same time being herbicide tolerant,for example Herculex I® (Dow AgroSciences, Pioneer Hi-BredInternational).

The term “useful plants” and/or “target crops” is to be understood asincluding also useful plants which have been so transformed by the useof recombinant DNA techniques that they are capable of synthesisingantipathogenic substances having a selective action, such as, forexample, the so-called “pathogenesis-related proteins” (PRPs, see e.g.EP-A-0 392 225). Examples of such antipathogenic substances andtransgenic plants capable of synthesising such antipathogenic substancesare known, for example, from EP-A-0 392 225, WO 95/33818, and EP-A-0 353191. The methods of producing such transgenic plants are generally knownto the person skilled in the art and are described, for example, in thepublications mentioned above.

Toxins that can be expressed by transgenic plants include, for example,insecticidal proteins from Bacillus cereus or Bacillus popilliae; orinsecticidal proteins from Bacillus thuringiensis, such as δ-endotoxins,e.g. Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, orvegetative insecticidal proteins (Vip), e.g. Vip1, Vip2, Vip3 or Vip3A;or insecticidal proteins of bacteria colonising nematodes, for examplePhotorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens,Xenorhabdus nematophilus; toxins produced by animals, such as scorpiontoxins, arachnid toxins, wasp toxins and other insect-specificneurotoxins; toxins produced by fungi, such as Streptomycetes toxins,plant lectins, such as pea lectins, barley lectins or snowdrop lectins;agglutinins; proteinase inhibitors, such as trypsin inhibitors, serineprotease inhibitors, patatin, cystatin, papain inhibitors;ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin,luffin, saporin or bryodin; steroid metabolism enzymes, such as3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl-transferase,cholesterol oxidases, ecdysone inhibitors, HMG-COA-reductase, ionchannel blockers, such as blockers of sodium or calcium channels,juvenile hormone esterase, diuretic hormone receptors, stilbenesynthase, bibenzyl synthase, chitinases and glucanases.

Further, in the context of the present invention there are to beunderstood by δ-endotoxins, for example Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2,Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins(Vip), for example Vip1, Vip2, Vip3 or Vip3A, expressly also hybridtoxins, truncated toxins and modified toxins. Hybrid toxins are producedrecombinantly by a new combination of different domains of thoseproteins (see, for example, WO 02/15701). Truncated toxins, for examplea truncated Cry1Ab, are known. In the case of modified toxins, one ormore amino acids of the naturally occurring toxin are replaced. In suchamino acid replacements, preferably non-naturally present proteaserecognition sequences are inserted into the toxin, such as, for example,in the case of Cry3A055, a cathepsin-G-recognition sequence is insertedinto a Cry3A toxin (see WO03/018810).

More examples of such toxins or transgenic plants capable ofsynthesising such toxins are disclosed, for example, in EP-A-0 374 753,WO93/07278, WO95/34656, EP-A-0 427 529, EP-A-451 878 and WO03/052073.

The processes for the preparation of such transgenic plants aregenerally known to the person skilled in the art and are described, forexample, in the publications mentioned above. Cry1-type deoxyribonucleicacids and their preparation are known, for example, from WO 95/34656,EP-A-0 367 474, EP-A-0 401 979 and WO 90/13651.

The toxin contained in the transgenic plants imparts to the plantstolerance to harmful insects. Such insects can occur in any taxonomicgroup of insects, but are especially commonly found in the beetles(Coleoptera), two-winged insects (Diptera) and butterflies(Lepidoptera).

Transgenic plants containing one or more genes that code for aninsecticidal resistance and express one or more toxins are known andsome of them are commercially available. Examples of such plants are:YieldGard® (maize variety that expresses a Cry1Ab toxin); YieldGardRootworm® (maize variety that expresses a Cry3Bb1 toxin); YieldGardPlus® (maize variety that expresses a Cry1Ab and a Cry3Bb1 toxin);Starlink® (maize variety that expresses a Cry9C toxin); Herculex I®(maize variety that expresses a Cry1Fa2 toxin and the enzymephosphinothricine N-acetyltransferase (PAT) to achieve tolerance to theherbicide glufosinate ammonium); NuCOTN 33B® (cotton variety thatexpresses a Cry1Ac toxin); Bollgard I® (cotton variety that expresses aCry1Ac toxin); Bollgard II® (cotton variety that expresses a Cry1Ac anda Cry2Ab toxin); VipCot® (cotton variety that expresses a Vip3A and aCry1Ab toxin); NewLeaf® (potato variety that expresses a Cry3A toxin);NatureGard®, Agrisure® GT Advantage (GA21 glyphosate-tolerant trait),Agrisure® CB Advantage (Bt11 corn borer (CB) trait) and Protecta®.

Further examples of such transgenic crops are:

1. Bt11 Maize from Syngenta Seeds SAS, Chemin de I′Hobit 27, F-31 790St. Sauveur, France, registration number C/FR/96/05/10. Geneticallymodified Zea mays which has been rendered resistant to attack by theEuropean corn borer (Ostrinia nubilalis and Sesamia nonagrioides) bytransgenic expression of a truncated Cry1Ab toxin. Bt11 maize alsotransgenically expresses the enzyme PAT to achieve tolerance to theherbicide glufosinate ammonium.

2. Bt176 Maize from Syngenta Seeds SAS, Chemin de I′Hobit 27, F-31 790St. Sauveur, France, registration number C/FR/96/05/10. Geneticallymodified Zea mays which has been rendered resistant to attack by theEuropean corn borer (Ostrinia nubilalis and Sesamia nonagrioides) bytransgenic expression of a Cry1Ab toxin. Bt176 maize also transgenicallyexpresses the enzyme PAT to achieve tolerance to the herbicideglufosinate ammonium.

3. MIR604 Maize from Syngenta Seeds SAS, Chemin de I′Hobit 27, F-31 790St. Sauveur, France, registration number C/FR/96/05/10. Maize which hasbeen rendered insect-resistant by transgenic expression of a modifiedCry3A toxin. This toxin is Cry3A055 modified by insertion of acathepsin-G-protease recognition sequence. The preparation of suchtransgenic maize plants is described in WO 03/018810.

4. MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren,B-1150 Brussels, Belgium, registration number C/DE/02/9. MON 863expresses a Cry3Bb1 toxin and has resistance to certain Coleopterainsects.

5. IPC 531 Cotton from Monsanto Europe S.A. 270-272 Avenue de Tervuren,B-1150 Brussels, Belgium, registration number C/ES/96/02.

6. 1507 Maize from Pioneer Overseas Corporation, Avenue Tedesco, 7B-1160 Brussels, Belgium, registration number C/NL/00/10. Geneticallymodified maize for the expression of the protein Cry1F for achievingresistance to certain Lepidoptera insects and of the PAT protein forachieving tolerance to the herbicide glufosinate ammonium.

7. NK603×MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue deTervuren, B-1150 Brussels, Belgium, registration number C/GB/02/M3/03.Consists of conventionally bred hybrid maize varieties by crossing thegenetically modified varieties NK603 and MON 810. NK603×MON 810 Maizetransgenically expresses the protein CP4 EPSPS, obtained fromAgrobacterium sp. strain CP4, which imparts tolerance to the herbicideRoundup® (contains glyphosate), and also a Cry1Ab toxin obtained fromBacillus thuringiensis subsp. kurstaki which brings about tolerance tocertain Lepidoptera, include the European corn borer.

The term “locus” as used herein means fields in or on which plants aregrowing, or where seeds of cultivated plants are sown, or where seedwill be placed into the soil. It includes soil, seeds, and seedlings, aswell as established vegetation.

The term “plants” refers to all physical parts of a plant, includingseeds, seedlings, saplings, roots, tubers, stems, stalks, foliage, andfruits.

The term “plant propagation material” is understood to denote generativeparts of the plant, such as seeds, which can be used for themultiplication of the latter, and vegetative material, such as cuttingsor tubers, for example potatoes. There may be mentioned for exampleseeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes andparts of plants. Germinated plants and young plants which are to betransplanted after germination or after emergence from the soil, mayalso be mentioned. These young plants may be protected beforetransplantation by a total or partial treatment by immersion. Preferably“plant propagation material” is understood to denote seeds.

Pesticidal agents referred to herein using their common name are known,for example, from “The Pesticide Manual”, 15th Ed., British CropProtection Council 2009.

The compounds of formula (I) may be used in unmodified form or,preferably, together with the adjuvants conventionally employed in theart of formulation. To this end they may be conveniently formulated inknown manner to emulsifiable concentrates, coatable pastes, directlysprayable or dilutable solutions or suspensions, dilute emulsions,wettable powders, soluble powders, dusts, granulates, and alsoencapsulations e.g. in polymeric substances. As with the type of thecompositions, the methods of application, such as spraying, atomising,dusting, scattering, coating or pouring, are chosen in accordance withthe intended objectives and the prevailing circumstances. Thecompositions may also contain further adjuvants such as stabilizers,antifoams, viscosity regulators, binders or tackifiers as well asfertilizers, micronutrient donors or other formulations for obtainingspecial effects.

Suitable carriers and adjuvants, e.g. for agricultural use, can be solidor liquid and are substances useful in formulation technology, e.g.natural or regenerated mineral substances, solvents, dispersants,wetting agents, tackifiers, thickeners, binders or fertilizers. Suchcarriers are for example described in WO 97/33890.

Suspension concentrates are aqueous formulations in which finely dividedsolid particles of the active compound are suspended. Such formulationsinclude anti-settling agents and dispersing agents and may furtherinclude a wetting agent to enhance activity as well an anti-foam and acrystal growth inhibitor. In use, these concentrates are diluted inwater and normally applied as a spray to the area to be treated. Theamount of active ingredient may range from 0.5% to 95% of theconcentrate.

Wettable powders are in the form of finely divided particles whichdisperse readily in water or other liquid carriers. The particlescontain the active ingredient retained in a solid matrix. Typical solidmatrices include fuller's earth, kaolin clays, silicas and other readilywet organic or inorganic solids. Wettable powders normally contain from5% to 95% of the active ingredient plus a small amount of wetting,dispersing or emulsifying agent.

Emulsifiable concentrates are homogeneous liquid compositionsdispersible in water or other liquid and may consist entirely of theactive compound with a liquid or solid emulsifying agent, or may alsocontain a liquid carrier, such as xylene, heavy aromatic naphthas,isophorone and other non-volatile organic solvents. In use, theseconcentrates are dispersed in water or other liquid and normally appliedas a spray to the area to be treated. The amount of active ingredientmay range from 0.5% to 95% of the concentrate.

Granular formulations include both extrudates and relatively coarseparticles and are usually applied without dilution to the area in whichtreatment is required. Typical carriers for granular formulationsinclude sand, fuller's earth, attapulgite clay, bentonite clays,montmorillonite clay, vermiculite, perlite, calcium carbonate, brick,pumice, pyrophyllite, kaolin, dolomite, plaster, wood flour, ground corncobs, ground peanut hulls, sugars, sodium chloride, sodium sulphate,sodium silicate, sodium borate, magnesia, mica, iron oxide, zinc oxide,titanium oxide, antimony oxide, cryolite, gypsum, diatomaceous earth,calcium sulphate and other organic or inorganic materials which absorbor which can be coated with the active compound. Granular formulationsnormally contain 5% to 25% of active ingredients which may includesurface-active agents such as heavy aromatic naphthas, kerosene andother petroleum fractions, or vegetable oils; and/or stickers such asdextrins, glue or synthetic resins.

Dusts are free-flowing admixtures of the active ingredient with finelydivided solids such as talc, clays, flours and other organic andinorganic solids which act as dispersants and carriers.

Microcapsules are typically droplets or granules of the activeingredient enclosed in an inert porous shell which allows escape of theenclosed material to the surroundings at controlled rates. Encapsulateddroplets are typically 1 to 50 microns in diameter. The enclosed liquidtypically constitutes 50 to 95% of the weight of the capsule and mayinclude solvent in addition to the active compound. Encapsulatedgranules are generally porous granules with porous membranes sealing thegranule pore openings, retaining the active species in liquid forminside the granule pores. Granules typically range from 1 millimetre to1 centimetre and preferably 1 to 2 millimetres in diameter. Granules areformed by extrusion, agglomeration or prilling, or are naturallyoccurring. Examples of such materials are vermiculite, sintered clay,kaolin, attapulgite clay, sawdust and granular carbon. Shell or membranematerials include natural and synthetic rubbers, cellulosic materials,styrene-butadiene copolymers, polyacrylonitriles, polyacrylates,polyesters, polyamides, polyureas, polyurethanes and starch xanthates.

Other useful formulations for agrochemical applications include simplesolutions of the active ingredient in a solvent in which it iscompletely soluble at the desired concentration, such as acetone,alkylated naphthalenes, xylene and other organic solvents. Pressurisedsprayers, wherein the active ingredient is dispersed in finely-dividedform as a result of vaporisation of a low boiling dispersant solventcarrier, may also be used.

Suitable agricultural adjuvants and carriers that are useful informulating the compositions of the invention in the formulation typesdescribed above are well known to those skilled in the art.

Liquid carriers that can be employed include, for example, water,toluene, xylene, petroleum naphtha, crop oil, acetone, methyl ethylketone, cyclohexanone, acetic anhydride, acetonitrile, acetophenone,amyl acetate, 2-butanone, chlorobenzene, cyclohexane, cyclohexanol,alkyl acetates, diacetonalcohol, 1,2-dichloropropane, diethanolamine,p-diethylbenzene, diethylene glycol, diethylene glycol abietate,diethylene glycol butyl ether, diethylene glycol ethyl ether, diethyleneglycol methyl ether, N,N-dimethyl formamide, dimethyl sulfoxide,1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether,dipropylene glycol dibenzoate, diproxitol, alkyl pyrrolidinone, ethylacetate, 2-ethyl hexanol, ethylene carbonate, 1,1,1-trichloroethane,2-heptanone, alpha pinene, d-limonene, ethylene glycol, ethylene glycolbutyl ether, ethylene glycol methyl ether, gamma-butyrolactone,glycerol, glycerol diacetate, glycerol monoacetate, glycerol triacetate,hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate,isooctane, isophorone, isopropyl benzene, isopropyl myristate, lacticacid, laurylamine, mesityl oxide, methoxy-propanol, methyl isoamylketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyloleate, methylene chloride, m-xylene, n-hexane, n-octylamine,octadecanoic acid, octyl amine acetate, oleic acid, oleylamine,o-xylene, phenol, polyethylene glycol (PEG400), propionic acid,propylene glycol, propylene glycol monomethyl ether, p-xylene, toluene,triethyl phosphate, triethylene glycol, xylene sulfonic acid, paraffin,mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amylacetate, butyl acetate, methanol, ethanol, isopropanol, and highermolecular weight alcohols such as amyl alcohol, tetrahydrofurfurylalcohol, hexanol, octanol, etc., ethylene glycol, propylene glycol,glycerine and N-methyl-2-pyrrolidinone. Water is generally the carrierof choice for the dilution of concentrates.

Suitable solid carriers include, for example, talc, titanium dioxide,pyrophyllite clay, silica, attapulgite clay, kieselguhr, chalk,diatomaxeous earth, lime, calcium carbonate, bentonite clay, fuller'searth, cotton seed hulls, wheat flour, soybean flour, pumice, woodflour, walnut shell flour and lignin.

A broad range of surface-active agents are advantageously employed inboth said liquid and solid compositions, especially those designed to bediluted with carrier before application. These agents, when used,normally comprise from 0.1% to 15% by weight of the formulation. Theycan be anionic, cationic, non-ionic or polymeric in character and can beemployed as emulsifying agents, wetting agents, suspending agents or forother purposes. Typical surface active agents include salts of alkylsulfates, such as diethanolammonium lauryl sulphate; alkylarylsulfonatesalts, such as calcium dodecylbenzenesulfonate; alkylphenol-alkyleneoxide addition products, such as nonylphenol-C.sub. 18 ethoxylate;alcohol-alkylene oxide addition products, such as tridecylalcohol-C.sub. 16 ethoxylate; soaps, such as sodium stearate;alkylnaphthalenesulfonate salts, such as sodiumdibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts,such as sodium di(2-ethylhexyl) sulfosuccinate; sorbitol esters, such assorbitol oleate; quaternary amines, such as lauryl trimethylammoniumchloride; polyethylene glycol esters of fatty acids, such aspolyethylene glycol stearate; block copolymers of ethylene oxide andpropylene oxide; and salts of mono and dialkyl phosphate esters.

Other adjuvants commonly utilized in agricultural compositions includecrystallisation inhibitors, viscosity modifiers, suspending agents,spray droplet modifiers, pigments, antioxidants, foaming agents,anti-foaming agents, light-blocking agents, compatibilizing agents,antifoam agents, sequestering agents, neutralising agents and buffers,corrosion inhibitors, dyes, odorants, spreading agents, penetrationaids, micronutrients, emollients, lubricants and sticking agents.

In addition, further, other biocidally active ingredients orcompositions may be combined with the compositions of the invention andused in the methods of the invention and applied simultaneously orsequentially with the compositions of the invention. When appliedsimultaneously, these further active ingredients may be formulatedtogether with the compositions of the invention or mixed in, forexample, the spray tank. These further biocidally active ingredients maybe fungicides, herbicides, insecticides, bactericides, acaricides,nematicides and/or plant growth regulators.

In addition, the compositions of the invention may also be applied withone or more systemically acquired resistance inducers (“SAR” inducer).SAR inducers are known and described in, for example, U.S. Pat. No.6,919,298 and include, for example, salicylates and the commercial SARinducer acibenzolar-S-methyl.

The compounds of formula (I) are normally used in the form ofcompositions and can be applied to the crop area or plant to be treated,simultaneously or in succession with further compounds. These furthercompounds can be e.g. fertilizers or micronutrient donors or otherpreparations, which influence the growth of plants. They can also beselective herbicides or non-selective herbicides as well asinsecticides, fungicides, bactericides, nematicides, molluscicides ormixtures of several of these preparations, if desired together withfurther carriers, surfactants or application promoting adjuvantscustomarily employed in the art of formulation.

The compounds of formula (I) may be used in the form of (fungicidal)compositions for controlling or protecting against phytopathogenicmicroorganisms, comprising as active ingredient at least one compound offormula (I) or of at least one preferred individual compound asabove-defined, in free form or in agrochemically usable salt form, andat least one of the above-mentioned adjuvants.

The invention therefore provides a composition, preferably a fungicidalcomposition, comprising at least one compound formula (I) anagriculturally acceptable carrier and optionally an adjuvant. Anagricultural acceptable carrier is for example a carrier that issuitable for agricultural use. Agricultural carriers are well known inthe art. Preferably said composition may comprise at least one or morepesticidally active compounds, for example an additional fungicidalactive ingredient in addition to the compound of formula (I).

The compound of formula (I) may be the sole active ingredient of acomposition or it may be admixed with one or more additional activeingredients such as a pesticide, fungicide, synergist, herbicide orplant growth regulator where appropriate. An additional activeingredient may, in some cases, result in unexpected synergisticactivities.

Examples of suitable additional active ingredients include thefollowing: 1,2,4-thiadiazoles, 2,6-dinitroanilines, acylalanines,aliphatic nitrogenous compounds, amidines, aminopyrimidinols, anilides,anilino-pyrimidines, anthraquinones, antibiotics, aryl-phenylketones,benzamides, benzene-sulfonamides, benzimidazoles, benzothiazoles,benzothiodiazoles, benzothiophenes, benzoylpyridines, benzthiadiazoles,benzylcarbamates, butylamines, carbamates, carboxamides, carpropamids,chloronitriles, cinnamic acid amides, copper containing compounds,cyanoacetamideoximes, cyanoacrylates, cyanoimidazoles,cyanomethylene-thiazolidines, dicarbonitriles, dicarboxamides,dicarboximides, dimethylsulphamates, dinitrophenol carbonates,dinitrophenysl, dinitrophenyl crotonates, diphenyl phosphates, dithiinocompounds, dithiocarbamates, dithioethers, dithiolanes,ethyl-amino-thiazole carboxamides, ethyl-phosphonates, furancarboxamides, glucopyranosyls, glucopyranoxyls, glutaronitriles,guanidines, herbicides/plant growth regulatosr, hexopyranosylantibiotics, hydroxy(2-amino)pyrimidines, hydroxyanilides,hydroxyisoxazoles, imidazoles, imidazolinones, insecticides/plant growthregulators, isobenzofuranones, isoxazolidinyl-pyridines, isoxazolines,maleimides, mandelic acid amides, mectin derivatives, morpholines,norpholines, n-phenyl carbamates, organotin compounds, oxathiincarboxamides, oxazoles, oxazolidine-diones, phenols, phenoxy quinolines,phenyl-acetamides, phenylamides, phenylbenzamides,phenyl-oxo-ethyl-thiophenes amides, phenylpyrroles, phenylureas,phosphorothiolates, phosphorus acids, phthalamic acids, phthalimides,picolinamides, piperazines, piperidines, plant extracts, polyoxins,propionamides, pthalimides, pyrazole-4-carboxamides, pyrazolinones,pyridazinones, pyridines, pyridine carboxamides, pyridinyl-ethylbenzamides, pyrimdinamines, pyrimidines, pyrimidine-amines,pyrimidione-hydrazone, pyrrolidines, pyrrolquinoliones, quinazolinones,quinolines, quinoline derivatives, quinoline-7-carboxylic acids,quinoxalines, spiroketalamines, strobilurins, sulfamoyl triazoles,sulphamides, tetrazolyloximes, thiadiazines, thiadiazole carboxamides,thiazole carboxanides, thiocyanates, thiophene carboxamides, toluamides,triazines, triazobenthiazoles, triazoles, triazole-thiones,triazolo-pyrimidylamine, valinamide carbamates, ammonium methylphosphonates, arsenic-containing compounds, benyimidazolylcarbamates,carbonitriles, carboxanilides, carboximidamides, carboxylicphenylamides, diphenyl pyridines, furanilides, hydrazine carboxamides,imidazoline acetates, isophthalates, isoxazolones, mercury salts,organomercury compounds, organophosphates, oxazolidinediones,pentylsulfonyl benzenes, phenyl benzamides, phosphonothionates,phosphorothioates, pyridyl carboxamides, pyridyl furfuryl ethers,pyridyl methyl ethers, SDHIs, thiadiazinanethiones, thiazolidines.

Examples of suitable additional active ingredients also include thefollowing: 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid(9-dichloromethylene-1,2,3,4-tetrahydro-1,4-methano-naphthalen-5-yl)-amide,3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acidmethoxy[1-methyl-2-(2,4,6-trichlorophenyl)-ethyl]-amide,1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxylic acid(2-dichloromethylene-3-ethyl-1-methyl-indan-4-yl)-amide (1072957-71-1),1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxylic acid(4′-methylsulfanyl-biphenyl-2-yl)-amide,1-methyl-3-difluoromethyl-4H-pyrazole-4-carboxylic acid[2-(2,4-dichloro-phenyl)-2-methoxy-1-methyl-ethyl]amide,(5-Chloro-2,4-dimethyl-pyridin-3-yl)-(2,3,4-trimethoxy-6-methyl-phenyl)-methanone,(5-Bromo-4-chloro-2-methoxy-pyridin-3-yl)-(2,3,4-trimethoxy-6-methyl-phenyl)-methanone,2-{2-[(E)-3-(2,6-Dichloro-phenyl)-1-methyl-prop-2-en-(E)-ylideneaminooxymethyl]-phenyl}-2-[(Z)-methoxyimino]-N-methyl-acetamide,3-[5-(4-Chloro-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine,(E)-N-methyl-2-[2-(2,5-dimethylphenoxymethyl)phenyl]-2-methoxy-iminoacetamide, 4-bromo-2-cyano-N,N-dimethyl-6-trifluoromethylbenzimidazole-1-sulphonamide,α-[N-(3-chloro-2,6-xylyl)-2-methoxyacetamido]-y-butyrolactone,4-chloro-2-cyano-N,N-dimethyl-5-p-tolylimidazole-1-sulfonamide,N-allyl-4, 5,-dimethyl-2-trimethylsilylthiophene-3-carboxamide,N-(1-cyano-1, 2-dimethylpropyl)-2-(2, 4-dichlorophenoxy) propionamide,N-(2-methoxy-5-pyridyl)-cyclopropane carboxamide,(.+−.)-cis-1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-cycloheptanol,2-(1-tert-butyl)-1-(2-chlorophenyl)-3-(1,2,4-triazol-1-yl)-propan-2-ol,2′,6′-dibromo-2-methyl-4-trifluoromethoxy-4′-trifluoromethyl-1,3-thiazole-5-carboxanilide,1-imidazolyl-1-(4′-chlorophenoxy)-3,3-dimethylbutan-2-one, methyl(E)-2-[2-[6-(2-cyanophenoxy)pyrimidin-4-yloxy]phenyl]3-methoxyacrylate,methyl(E)-2-[2-[6-(2-thioamidophenoxy)pyrimidin-4-yloxy]phenyl]-3-methoxyacrylate,methyl(E)-2-[2-[6-(2-fluorophenoxy)pyrimidin-4-yloxy]phenyl]-3-methoxyacrylate,methyl(E)-2-[2-[6-(2,6-difluorophenoxy)pyrimidin-4-yloxy]phenyl]-3-methoxyacrylate,methyl (E)-2-[2-[3-(pyrimidin-2-yloxy)phenoxy]phenyl]-3-methoxyacrylate,methyl(E)-2-[2-[3-(5-methylpyrimidin-2-yloxy)-phenoxy]phenyl]-3-methoxyacrylate,methyl(E)-2-[2-[3-(phenyl-sulphonyloxy)phenoxy]phenyl-3-methoxyacrylate,methyl (E)-2-[2-[3-(4-nitrophenoxy)phenoxy]phenyl]-3-methoxyacrylate,methyl (E)-2-[2-phenoxyphenyl]-3-methoxyacrylate, methyl(E)-2-[2-(3,5-dimethyl-benzoyl)pyrrol-1-yl]-3-methoxyacrylate, methyl(E)-2-[2-(3-methoxyphenoxy)phenyl]-3-methoxyacrylate, methyl(E)-2[2-(2-phenylethen-1-yl)-phenyl]-3-methoxyacrylate, methyl(E)-2-[2-(3,5-dichlorophenoxy)pyridin-3-yl]-3-methoxyacrylate, methyl(E)-2-(2-(3-(1,1,2,2-tetrafluoroethoxy)phenoxy)phenyl)-3-methoxyacrylate,methyl(E)-2-(2-[3-(alpha-hydroxybenzyl)phenoxy]phenyl)-3-methoxyacrylate,methyl (E)-2-(2-(4-phenoxypyridin-2-yloxy)phenyl)-3-methoxyacrylate,methyl (E)-2-[2-(3-n-propyloxy-phenoxy)phenyl]3-methoxyacrylate, methyl(E)-2-[2-(3-isopropyloxyphenoxy)phenyl]-3-methoxyacrylate, methyl(E)-2-[2-[3-(2-fluorophenoxy)phenoxy]phenyl]-3-methoxyacrylate, methyl(E)-2-[2-(3-ethoxyphenoxy)phenyl]-3-methoxyacrylate, methyl(E)-2-[2-(4-tert-butyl-pyridin-2-yloxy)phenyl]-3-methoxyacrylate, methyl(E)-2-[2-[3-(3-cyanophenoxy)phenoxy]phenyl]-3-methoxyacrylate, methyl(E)-2-[2-[(3-methyl-pyridin-2-yloxymethyl)phenyl]-3-methoxyacrylate,methyl(E)-2-[2-[6-(2-methyl-phenoxy)pyrimidin-4-yloxy]phenyl]-3-methoxyacrylate,methyl(E)-2-[2-(5-bromo-pyridin-2-yloxymethyl)phenyl]-3-methoxyacrylate,methyl(E)-2-[2-(3-(3-iodopyridin-2-yloxy)phenoxy)phenyl]-3-methoxyacrylate,methyl(E)-2-[2-[6-(2-chloropyridin-3-yloxy)pyrimidin-4-yloxy]phenyl]-3-methoxyacrylate,methyl(E),(E)-2-[2-(5,6-dimethylpyrazin-2-ylmethyloximinomethyl)phenyl]-3-methoxyacrylate,methyl(E)-2-{2-[6-(6-methylpyridin-2-yloxy)pyrimidin-4-yloxy]phenyl}-3-methoxy-acrylate,methyl(E),(E)-2-{2-(3-methoxyphenyl)methyloximinomethyl]-phenyl}-3-methoxyacrylate,methyl(E)-2-{2-(6-(2-azidophenoxy)-pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate,methyl(E),(E)-2-{2-[6-phenylpyrimidin-4-yl)-methyloximinomethyl]phenyl}-3-methoxyacrylate,methyl(E),(E)-2-{2-[(4-chlorophenyl)-methyloximinomethyl]-phenyl}-3-methoxyacrylate,methyl(E)-2-{2-[6-(2-n-propylphenoxy)-1,3,5-triazin-4-yloxy]phenyl}-3-methoxyacrylate,methyl(E),(E)-2-{2-[(3-nitrophenyl)methyloximinomethyl]phenyl}-3-methoxyacrylate,3-chloro-7-(2-aza-2,7,7-trimethyl-oct-3-en-5-ine),2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide, 3-iodo-2-propinylalcohol, 4-chlorophenyl-3-iodopropargyl formal,3-bromo-2,3-diiodo-2-propenyl ethylcarbamate, 2,3,3-triiodoallylalcohol, 3-bromo-2,3-diiodo-2-propenyl alcohol, 3-iodo-2-propinyln-butylcarbamate, 3-iodo-2-propinyl n-hexylcarbamate, 3-iodo-2-propinylcyclohexyl-carbamate, 3-iodo-2-propinyl phenylcarbamate; phenolderivatives, such as tribromophenol, tetrachlorophenol,3-methyl-4-chlorophenol, 3,5-dimethyl-4-chlorophenol, phenoxyethanol,dichlorophene, o-phenylphenol, m-phenylphenol, p-phenylphenol,2-benzyl-4-chlorophenol, 5-hydroxy-2(5H)-furanone;4,5-dichlorodithiazolinone, 4,5-benzodithiazolinone,4,5-trimethylenedithiazolinone, 4,5-dichloro-(3H)-1,2-dithiol-3-one,3,5-dimethyl-tetrahydro-1,3,5-thiadiazine-2-thione,N-(2-p-chlorobenzoylethyl)-hexaminium chloride, acibenzolar, acypetacs,alanycarb, albendazole, aldimorph, allicin, allyl alcohol, ametoctradin,amisulbrom, amobam, ampropylfos, anilazine, asomate, aureofungin,azaconazole, azafendin, azithiram, azoxystrobin, barium polysulfide,benalaxyl, benalaxyl-M, benodanil, benomyl, benquinox, bentaluron,benthiavalicarb, benthiazole, benzalkonium chloride, benzamacril,benzamorf, benzohydroxamic acid, benzovindiflupyr, berberine,bethoxazin, biloxazol, binapacryl, biphenyl, bitertanol, bithionol,bixafen, blasticidin-S, boscalid, bromothalonil, bromuconazole,bupirimate, buthiobate, butylamine calcium polysulfide, captafol,captan, carbamorph, carbendazim, carbendazim chlorhydrate, carboxin,carpropamid, carvone, CGA41396, CGA41397, chinomethionate, chitosan,chlobenthiazone, chloraniformethan, chloranil, chlorfenazole, chloroneb,chloropicrin, chlorothalonil, chlorozolinate, chlozolinate, climbazole,clotrimazole, clozylacon, copper containing compounds such as copperacetate, copper carbonate, copper hydroxide, copper naphthenate, copperoleate, copper oxychloride, copper oxyquinolate, copper silicate, coppersulphate, copper tallate, copper zinc chromate and Bordeaux mixture,cresol, cufraneb, cuprobam, cuprous oxide, cyazofamid, cyclafuramid,cycloheximide, cyflufenamid, cymoxanil, cypendazole, cyproconazole,cyprodinil, dazomet, debacarb, decafentin, dehydroacetic acid,di-2-pyridyl disulphide 1,1′-dioxide, dichlofluanid, diclomezine,dichlone, dicloran, dichlorophen, dichlozoline, diclobutrazol,diclocymet, diethofencarb, difenoconazole, difenzoquat, diflumetorim,O-di-iso-propyl-S-benzyl thiophosphate, dimefluazole, dimetachlone,dimetconazole, dimethomorph, dimethirimol, diniconazole, diniconazole-M,dinobuton, dinocap, dinocton, dinopenton, dinosulfon, dinoterbon,diphenylamine, dipyrithione, disulfiram, ditalimfos, dithianon,dithioether, dodecyl dimethyl ammonium chloride, dodemorph, dodicin,dodine, doguadine, drazoxolon, edifenphos, enestroburin, epoxiconazole,etaconazole, etem, ethaboxam, ethirimol, ethoxyquin, ethilicin, ethyl(Z)—N-benzyl-N([methyl (methyl-thioethylideneamino-oxycarbonyl) amino]thio)-ß-alaninate, etridiazole, famoxadone, fenamidone, fenaminosulf,fenapanil, fenarimol, fenbuconazole, fenfuram, fenhexamid, fenitropan,fenoxanil, fenpiclonil, fenpicoxamid, fenpropidin, fenpropimorph,fenpyrazamine, fentin acetate, fentin hydroxide, ferbam, ferimzone,fluazinam, fludioxonil, flumetover, flumorph, flupicolide, fluopyram,fluoroimide, fluotrimazole, fluoxastrobin, fluquinconazole, flusilazole,flusulfamide, flutanil, flutolanil, flutriafol, fluxapyroxad, folpet,formaldehyde, fosetyl, fuberidazole, furalaxyl, furametpyr, furcarbanil,furconazole, furfural, furmecyclox, furophanate, glyodin, griseofulvin,guazatine, halacrinate, hexachlorobenzene, hexachlorobutadiene,hexachlorophene, hexaconazole, hexylthiofos, hydrargaphen,hydroxyisoxazole, hymexazole, imazalil, imazalil sulphate,imibenconazole, iminoctadine, iminoctadine triacetate, inezin, iodocarb,ipconazole, ipfentrifluconazole, iprobenfos, iprodione, iprovalicarb,isopropanylbutyl carbamate, isoprothiolane, isopyrazam, isotianil,isovaledione, izopamfos, kasugamycin, kresoxim-methyl, LY186054,LY211795, LY248908, mancozeb, mandipropamid, maneb, mebenil,mecarbinzid, mefenoxam, mefentrifluconazole, mepanipyrim, mepronil,mercuric chloride, mercurous chloride, meptyldinocap, metalaxyl,metalaxyl-M, metam, metazoxolon, metconazole, methasulfocarb,methfuroxam, methyl bromide, methyl iodide, methyl isothiocyanate,metiram, metiram-zinc, metominostrobin, metrafenone, metsulfovax,milneb, moroxydine, myclobutanil, myclozolin, nabam, natamycin,neoasozin, nickel dimethyldithiocarbamate, nitrostyrene,nitrothal-iso-propyl, nuarimol, octhilinone, ofurace, organomercurycompounds, orysastrobin, osthol, oxadixyl, oxasulfuron, oxathiapiprolin,oxine-copper, oxolinic acid, oxpoconazole, oxycarboxin, parinol,pefurazoate, penconazole, pencycuron, penflufen, pentachlorophenol,penthiopyrad, phenamacril, phenazin oxide, phosdiphen, phosetyl-Al,phosphorus acids, phthalide, picoxystrobin, piperalin, polycarbamate,polyoxin D, polyoxrim, polyram, probenazole, prochloraz, procymidone,propamidine, propamocarb, propiconazole, propineb, propionic acid,proquinazid, prothiocarb, prothioconazole, pydiflumetofen, pyracarbolid,pyraclostrobin, pyrametrostrobin, pyraoxystrobin, pyrazophos,pyribencarb, pyridinitril, pyrifenox, pyrimethanil, pyriofenone,pyroquilon, pyroxychlor, pyroxyfur, pyrrolnitrin, quaternary ammoniumcompounds, quinacetol, quinazamid, quinconazole, quinomethionate,quinoxyfen, quintozene, rabenzazole, santonin, sedaxane, silthiofam,simeconazole, sipconazole, sodium pentachlorophenate, spiroxamine,streptomycin, sulphur, sultropen, tebuconazole, tebfloquin, tecloftalam,tecnazene, tecoram, tetraconazole, thiabendazole, thiadifluor,thicyofen, thifluzamide, 2-(thiocyanomethylthio) benzothiazole,thiophanate-methyl, thioquinox, thiram, tiadinil, timibenconazole,tioxymid, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol,triamiphos, triarimol, triazbutil, triazoxide, tricyclazole, tridemorph,trifloxystrobin, triflumazole, triforine, triflumizole, triticonazole,uniconazole, urbacide, validamycin, valifenalate, vapam, vinclozolin,zarilamid, zineb, ziram, and zoxamide.

The compounds of the invention may also be used in combination withanthelmintic agents. Such anthelmintic agents include, compoundsselected from the macrocyclic lactone class of compounds such asivermectin, avermectin, abamectin, emamectin, eprinomectin, doramectin,selamectin, moxidectin, nemadectin and milbemycin derivatives asdescribed in EP-357460, EP-444964 and EP-594291. Additional anthelminticagents include semisynthetic and biosynthetic avermectin/milbemycinderivatives such as those described in U.S. Pat. No. 5,015,630,WO-9415944 and WO-9522552. Additional anthelmintic agents include thebenzimidazoles such as albendazole, cambendazole, fenbendazole,flubendazole, mebendazole, oxfendazole, oxibendazole, parbendazole, andother members of the class. Additional anthelmintic agents includeimidazothiazoles and tetrahydropyrimidines such as tetramisole,levamisole, pyrantel pamoate, oxantel or morantel. Additionalanthelmintic agents include flukicides, such as triclabendazole andclorsulon and the cestocides, such as praziquantel and epsiprantel.

The compounds of the invention may be used in combination withderivatives and analogues of the paraherquamide/marcfortine class ofanthelmintic agents, as well as the antiparasitic oxazolines such asthose disclosed in U.S. Pat. Nos. 5,478,855, 4,639,771 and DE-19520936.

The compounds of the invention may be used in combination withderivatives and analogues of the general class of dioxomorpholineantiparasitic agents as described in WO 96/15121 and also withanthelmintic active cyclic depsipeptides such as those described in WO96/11945, WO 93/19053, WO 93/25543, EP 0 626 375, EP 0 382 173, WO94/19334, EP 0 382 173, and EP 0 503 538.

The compounds of the invention may be used in combination with otherectoparasiticides; for example, fipronil; pyrethroids; organophosphates;insect growth regulators such as lufenuron; ecdysone agonists such astebufenozide and the like; neonicotinoids such as imidacloprid and thelike.

The compounds of the invention may be used in combination with terpenealkaloids, for example those described in International PatentApplication Publication Numbers WO 95/19363 or WO 04/72086, particularlythe compounds disclosed therein.

Other examples of such biologically active compounds that the compoundsof the invention may be used in combination with include but are notrestricted to the following:

Organophosphates: acephate, azamethiphos, azinphos-ethyl,azinphos-methyl, bromophos, bromophos-ethyl, cadusafos, chlorethoxyphos,chlorpyrifos, chlorfenvinphos, chlormephos, demeton, demeton-S-methyl,demeton-S-methyl sulphone, dialifos, diazinon, dichlorvos, dicrotophos,dimethoate, disulfoton, ethion, ethoprophos, etrimfos, famphur,fenamiphos, fenitrothion, fensulfothion, fenthion, flupyrazofos,fonofos, formothion, fosthiazate, heptenophos, isazophos, isothioate,isoxathion, malathion, methacriphos, methamidophos, methidathion,methyl-parathion, mevinphos, monocrotophos, naled, omethoate,oxydemeton-methyl, paraoxon, parathion, parathion-methyl, phenthoate,phosalone, phosfolan, phosphocarb, phosmet, phosphamidon, phorate,phoxim, pirimiphos, pirimiphos-methyl, profenofos, propaphos,proetamphos, prothiofos, pyraclofos, pyridapenthion, quinalphos,sulprophos, temephos, terbufos, tebupirimfos, tetrachlorvinphos,thimeton, triazophos, trichlorfon, vamidothion.

Carbamates: alanycarb, aldicarb, 2-sec-butylphenyl methylcarbamate,benfuracarb, carbaryl, carbofuran, carbosulfan, cloethocarb,ethiofencarb, fenoxycarb, fenthiocarb, furathiocarb, HCN-801,isoprocarb, indoxacarb, methiocarb, methomyl,5-methyl-m-cumenylbutyryl(methyl)carbamate, oxamyl, pirimicarb,propoxur, thiodicarb, thiofanox, triazamate, UC-51717.

Pyrethroids: acrinathin, allethrin, alphametrin, 5-benzyl-3-furylmethyl(E)-(1R)-cis-2,2-dimethyl-3-(2-oxothiolan-3-ylidenemethyl)cyclopropanecarboxylate,bifenthrin, beta-cyfluthrin, cyfluthrin, a-cypermethrin,beta-cypermethrin, bioallethrin, bioallethrin((S)-cyclopentylisomer),bioresmethrin, bifenthrin, NCI-85193, cycloprothrin, cyhalothrin,cythithrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate,ethofenprox, fenfluthrin, fenpropathrin, fenvalerate, flucythrinate,flumethrin, fluvalinate (D isomer), imiprothrin, cyhalothrin,lambda-cyhalothrin, permethrin, phenothrin, prallethrin, pyrethrins(natural products), resmethrin, tetramethrin, transfluthrin,theta-cypermethrin, silafluofen, t-fluvalinate, tefluthrin,tralomethrin, Zeta-cypermethrin.

Arthropod growth regulators: a) chitin synthesis inhibitors:benzoylureas: chlorfluazuron, diflubenzuron, fluazuron, flucycloxuron,flufenoxuron, hexaflumuron, lufenuron, novaluron, teflubenzuron,triflumuron, buprofezin, diofenolan, hexythiazox, etoxazole,chlorfentazine; b) ecdysone antagonists: halofenozide, methoxyfenozide,tebufenozide; c) juvenoids: pyriproxyfen, methoprene (includingS-methoprene), fenoxycarb; d) lipid biosynthesis inhibitors:spirodiclofen.

Other antiparasitics: acequinocyl, amitraz, AKD-1022, ANS-118,azadirachtin, Bacillus thuringiensis, bensultap, bifenazate, binapacryl,bromopropylate, BTG-504, BTG-505, camphechlor, cartap, chlorobenzilate,chlordimeform, chlorfenapyr, chromafenozide, clothianidine, cyromazine,diacloden, diafenthiuron, DBI-3204, dinactin,dihydroxymethyldihydroxypyrrolidine, dinobuton, dinocap, endosulfan,ethiprole, ethofenprox, fenazaquin, flumite, MTI-800, fenpyroximate,fluacrypyrim, flubenzimine, flubrocythrinate, flufenzine, flufenprox,fluproxyfen, halofenprox, hydramethylnon, IKI-220, kanemite, NC-196,neem guard, nidinorterfuran, nitenpyram, SD-35651, WL-108477, pirydaryl,propargite, protrifenbute, pymethrozine, pyridaben, pyrimidifen,NC-1111, R-195, RH-0345, RH-2485, RYI-210, S-1283, S-1833, SI-8601,silafluofen, silomadine, spinosad, tebufenpyrad, tetradifon,tetranactin, thiacloprid, thiocyclam, thiamethoxam, tolfenpyrad,triazamate, triethoxyspinosyn, trinactin, verbutin, vertalec, YI-5301.

Biological agents: Bacillus thuringiensis ssp aizawai, kurstaki,Bacillus thuringiensis delta endotoxin, baculovirus, entomopathogenicbacteria, virus and fungi.

Bactericides: chlortetracycline, oxytetracycline, streptomycin.

Other biological agents: enrofloxacin, febantel, penethamate, moloxicam,cefalexin, kanamycin, pimobendan, clenbuterol, omeprazole, tiamulin,benazepril, pyriprole, cefquinome, florfenicol, buserelin, cefovecin,tulathromycin, ceftiour, carprofen, metaflumizone, praziquarantel,triclabendazole.

The following mixtures of the compounds of Formula (I) with activeingredients are preferred. The abbreviation “TX” means one compoundselected from the group consisting of the compounds as represented inTables A1 to A8 or Table B1 to B8 (above) or Table E or Table F or TableG (below):

an adjuvant selected from the group of substances consisting ofpetroleum oils (alternative name) (628)+TX,

an acaricide selected from the group of substances consisting of1,1-bis(4-chloro-phenyl)-2-ethoxyethanol (IUPAC name) (910)+TX,2,4-dichlorophenyl benzenesulfonate (IUPAC/Chemical Abstracts name)(1059)+TX, 2-fluoro-N-methyl-N-1-naphthylacetamide (IUPAC name)(1295)+TX, 4-chlorophenyl phenyl sulfone (IUPAC name) (981)+TX,abamectin (1)+TX, acequinocyl (3)+TX, acetoprole [CCN]+TX, acrinathrin(9)+TX, aldicarb (16)+TX, aldoxycarb (863)+TX, alpha-cypermethrin(202)+TX, amidithion (870)+TX, amidoflumet [CCN]+TX, amidothioate(872)+TX, amiton (875)+TX, amiton hydrogen oxalate (875)+TX, amitraz(24)+TX, aramite (881)+TX, arsenous oxide (882)+TX, AVI 382 (compoundcode)+TX, AZ 60541 (compound code)+TX, azinphos-ethyl (44)+TX,azinphos-methyl (45)+TX, azobenzene (IUPAC name) (888)+TX, azocyclotin(46)+TX, azothoate (889)+TX, benomyl (62)+TX, benoxafos (alternativename) [CCN]+TX, benzoximate (71)+TX, benzyl benzoate (IUPAC name)[CCN]+TX, bifenazate (74)+TX, bifenthrin (76)+TX, binapacryl (907)+TX,brofenvalerate (alternative name)+TX, broflanilide [1207727-04-5]+TX,bromocyclen (918)+TX, bromophos (920)+TX, bromophos-ethyl (921)+TX,bromopropylate (94)+TX, buprofezin (99)+TX, butocarboxim (103)+TX,butoxycarboxim (104)+TX, butylpyridaben (alternative name)+TX, calciumpolysulfide (IUPAC name) (111)+TX, camphechlor (941)+TX, carbanolate(943)+TX, carbaryl (115)+TX, carbofuran (118)+TX, carbophenothion(947)+TX, CGA 50′439 (development code) (125)+TX, chinomethionat(126)+TX, chlorbenside (959)+TX, chlordimeform (964)+TX, chlordimeformhydrochloride (964)+TX, chlorfenapyr (130)+TX, chlorfenethol (968)+TX,chlorfenson (970)+TX, chlorfensulfide (971)+TX, chlorfenvinphos(131)+TX, chlorobenzilate (975)+TX, chloromebuform (977)+TX,chloromethiuron (978)+TX, chloropropylate (983)+TX, chlorpyrifos(145)+TX, chlorpyrifos-methyl (146)+TX, chlorthiophos (994)+TX, cinerinI (696)+TX, cinerin II (696)+TX, cinerins (696)+TX, clofentezine(158)+TX, closantel (alternative name) [CCN]+TX, coumaphos (174)+TX,crotamiton (alternative name) [CCN]+TX, crotoxyphos (1010)+TX, cufraneb(1013)+TX, cyanthoate (1020)+TX, cyflumetofen (CAS Reg. No.:400882-07-7)+TX, cyhalothrin (196)+TX, cyhexatin (199)+TX, cypermethrin(201)+TX, DCPM (1032)+TX, DDT (219)+TX, demephion (1037)+TX, demephion-O(1037)+TX, demephion-S(1037)+TX, demeton (1038)+TX, demeton-methyl(224)+TX, demeton-O (1038)+TX, demeton-O-methyl (224)+TX,demeton-S(1038)+TX, demeton-S-methyl (224)+TX, demeton-S-methylsulfon(1039)+TX, diafenthiuron (226)+TX, dialifos (1042)+TX, diazinon(227)+TX, dichlofluanid (230)+TX, dichlorvos (236)+TX, dicliphos(alternative name)+TX, dicofol (242)+TX, dicrotophos (243)+TX,dienochlor (1071)+TX, dimefox (1081)+TX, dimethoate (262)+TX, dinactin(alternative name) (653)+TX, dinex (1089)+TX, dinex-diclexine (1089)+TX,dinobuton (269)+TX, dinocap (270)+TX, dinocap-4 [CCN]+TX, dinocap-6[CCN]+TX, dinocton (1090)+TX, dinopenton (1092)+TX, dinosulfon(1097)+TX, dinoterbon (1098)+TX, dioxathion (1102)+TX, diphenyl sulfone(IUPAC name) (1103)+TX, disulfiram (alternative name) [CCN]+TX,disulfoton (278)+TX, DNOC (282)+TX, dofenapyn (1113)+TX, doramectin(alternative name) [CCN]+TX, endosulfan (294)+TX, endothion (1121)+TX,EPN (297)+TX, eprinomectin (alternative name) [CCN]+TX, ethion (309)+TX,ethoate-methyl (1134)+TX, etoxazole (320)+TX, etrimfos (1142)+TX,fenazaflor (1147)+TX, fenazaquin (328)+TX, fenbutatin oxide (330)+TX,fenothiocarb (337)+TX, fenpropathrin (342)+TX, fenpyrad (alternativename)+TX, fenpyroximate (345)+TX, fenson (1157)+TX, fentrifanil(1161)+TX, fenvalerate (349)+TX, fipronil (354)+TX, fluacrypyrim(360)+TX, fluazuron (1166)+TX, flubenzimine (1167)+TX, flucycloxuron(366)+TX, flucythrinate (367)+TX, fluenetil (1169)+TX, flufenoxuron(370)+TX, flumethrin (372)+TX, fluorbenside (1174)+TX, fluvalinate(1184)+TX, FMC 1137 (development code) (1185)+TX, formetanate (405)+TX,formetanate hydrochloride (405)+TX, formothion (1192)+TX, formparanate(1193)+TX, gamma-HCH (430)+TX, glyodin (1205)+TX, halfenprox (424)+TX,heptenophos (432)+TX, hexadecyl cyclopropanecarboxylate (IUPAC/ChemicalAbstracts name) (1216)+TX, hexythiazox (441)+TX, iodomethane (IUPACname) (542)+TX, isocarbophos (alternative name) (473)+TX, isopropylO-(methoxyaminothiophosphoryl)salicylate (IUPAC name) (473)+TX,ivermectin (alternative name) [CCN]+TX, jasmolin I (696)+TX, jasmolin II(696)+TX, jodfenphos (1248)+TX, lindane (430)+TX, lufenuron (490)+TX,malathion (492)+TX, malonoben (1254)+TX, mecarbam (502)+TX, mephosfolan(1261)+TX, mesulfen (alternative name) [CCN]+TX, methacrifos (1266)+TX,methamidophos (527)+TX, methidathion (529)+TX, methiocarb (530)+TX,methomyl (531)+TX, methyl bromide (537)+TX, metolcarb (550)+TX,mevinphos (556)+TX, mexacarbate (1290)+TX, milbemectin (557)+TX,milbemycin oxime (alternative name) [CCN]+TX, mipafox (1293)+TX,monocrotophos (561)+TX, morphothion (1300)+TX, moxidectin (alternativename) [CCN]+TX, naled (567)+TX, NC-184 (compound code)+TX, NC-512(compound code)+TX, nifluridide (1309)+TX, nikkomycins (alternativename) [CCN]+TX, nitrilacarb (1313)+TX, nitrilacarb 1:1 zinc chloridecomplex (1313)+TX, NNI-0101 (compound code)+TX, NNI-0250 (compoundcode)+TX, omethoate (594)+TX, oxamyl (602)+TX, oxydeprofos (1324)+TX,oxydisulfoton (1325)+TX, pp′-DDT (219)+TX, parathion (615)+TX,permethrin (626)+TX, petroleum oils (alternative name) (628)+TX,phenkapton (1330)+TX, phenthoate (631)+TX, phorate (636)+TX, phosalone(637)+TX, phosfolan (1338)+TX, phosmet (638)+TX, phosphamidon (639)+TX,phoxim (642)+TX, pirimiphos-methyl (652)+TX, polychloroterpenes(traditional name) (1347)+TX, polynactins (alternative name) (653)+TX,proclonol (1350)+TX, profenofos (662)+TX, promacyl (1354)+TX, propargite(671)+TX, propetamphos (673)+TX, propoxur (678)+TX, prothidathion(1360)+TX, prothoate (1362)+TX, pyrethrin I (696)+TX, pyrethrin II(696)+TX, pyrethrins (696)+TX, pyridaben (699)+TX, pyridaphenthion(701)+TX, pyrimidifen (706)+TX, pyrimitate (1370)+TX, quinalphos(711)+TX, quintiofos (1381)+TX, R-1492 (development code) (1382)+TX,RA-17 (development code) (1383)+TX, rotenone (722)+TX, schradan(1389)+TX, sebufos (alternative name)+TX, selamectin (alternative name)[CCN]+TX, SI-0009 (compound code)+TX, sophamide (1402)+TX, spirodiclofen(738)+TX, spiromesifen (739)+TX, SSI-121 (development code) (1404)+TX,sulfiram (alternative name) [CCN]+TX, sulfluramid (750)+TX, sulfotep(753)+TX, sulfur (754)+TX, SZI-121 (development code) (757)+TX,tau-fluvalinate (398)+TX, tebufenpyrad (763)+TX, TEPP (1417)+TX, terbam(alternative name)+TX, tetrachlorvinphos (777)+TX, tetradifon (786)+TX,tetranactin (alternative name) (653)+TX, tetrasul (1425)+TX, thiafenox(alternative name)+TX, thiocarboxime (1431)+TX, thiofanox (800)+TX,thiometon (801)+TX, thioquinox (1436)+TX, thuringiensin (alternativename) [CCN]+TX, triamiphos (1441)+TX, triarathene (1443)+TX, triazophos(820)+TX, triazuron (alternative name)+TX, trichlorfon (824)+TX,trifenofos (1455)+TX, trinactin (alternative name) (653)+TX, vamidothion(847)+TX, vaniliprole [CCN] and YI-5302 (compound code)+TX,

an algicide selected from the group of substances consisting ofbethoxazin [CCN]+TX, copper dioctanoate (IUPAC name) (170)+TX, coppersulfate (172)+TX, cybutryne [CCN]+TX, dichlone (1052)+TX, dichlorophen(232)+TX, endothal (295)+TX, fentin (347)+TX, hydrated lime [CCN]+TX,nabam (566)+TX, quinoclamine (714)+TX, quinonamid (1379)+TX, simazine(730)+TX, triphenyltin acetate (IUPAC name) (347) and triphenyltinhydroxide (IUPAC name) (347)+TX,

an anthelmintic selected from the group of substances consisting ofabamectin (1)+TX, crufomate (1011)+TX, doramectin (alternative name)[CCN]+TX, emamectin (291)+TX, emamectin benzoate (291)+TX, eprinomectin(alternative name) [CCN]+TX, ivermectin (alternative name) [CCN]+TX,milbemycin oxime (alternative name) [CCN]+TX, moxidectin (alternativename) [CCN]+TX, piperazine [CCN]+TX, selamectin (alternative name)[CCN]+TX, spinosad (737) and thiophanate (1435)+TX,

an avicide selected from the group of substances consisting ofchloralose (127)+TX, endrin (1122)+TX, fenthion (346)+TX,pyridin-4-amine (IUPAC name) (23) and strychnine (745)+TX,

a bactericide selected from the group of substances consisting of1-hydroxy-1H-pyridine-2-thione (IUPAC name) (1222)+TX,4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748)+TX,8-hydroxyquinoline sulfate (446)+TX, bronopol (97)+TX, copperdioctanoate (IUPAC name) (170)+TX, copper hydroxide (IUPAC name)(169)+TX, cresol [CCN]+TX, dichlorophen (232)+TX, dipyrithione(1105)+TX, dodicin (1112)+TX, fenaminosulf (1144)+TX, formaldehyde(404)+TX, hydrargaphen (alternative name) [CCN]+TX, kasugamycin(483)+TX, kasugamycin hydrochloride hydrate (483)+TX, nickelbis(dimethyldithiocarbamate) (IUPAC name) (1308)+TX, nitrapyrin(580)+TX, octhilinone (590)+TX, oxolinic acid (606)+TX, oxytetracycline(611)+TX, potassium hydroxyquinoline sulfate (446)+TX, probenazole(658)+TX, streptomycin (744)+TX, streptomycin sesquisulfate (744)+TX,tecloftalam (766)+TX, and thiomersal (alternative name) [CCN]+TX,

a biological agent selected from the group of substances consisting ofAdoxophyes orana GV (alternative name) (12)+TX, Agrobacteriumradiobacter (alternative name) (13)+TX, Amblyseius spp. (alternativename) (19)+TX, Anagrapha falcifera NPV (alternative name) (28)+TX,Anagrus atomus (alternative name) (29)+TX, Aphelinus abdominalis(alternative name) (33)+TX, Aphidius colemani (alternative name)(34)+TX, Aphidoletes aphidimyza (alternative name) (35)+TX, Autographacalifornica NPV (alternative name) (38)+TX, Bacillus firmus (alternativename) (48)+TX, Bacillus sphaericus Neide (scientific name) (49)+TX,Bacillus thuringiensis Berliner (scientific name) (51)+TX, Bacillusthuringiensis subsp. aizawai (scientific name) (51)+TX, Bacillusthuringiensis subsp. israelensis (scientific name) (51)+TX, Bacillusthuringiensis subsp. japonensis (scientific name) (51)+TX, Bacillusthuringiensis subsp. kurstaki (scientific name) (51)+TX, Bacillusthuringiensis subsp. tenebrionis (scientific name) (51)+TX, Beauveriabassiana (alternative name) (53)+TX, Beauveria brongniartii (alternativename) (54)+TX, Chrysoperla carnea (alternative name) (151)+TX,Cryptolaemus montrouzieri (alternative name) (178)+TX, Cydia pomonellaGV (alternative name) (191)+TX, Dacnusa sibirica (alternative name)(212)+TX, Diglyphus isaea (alternative name) (254)+TX, Encarsia formosa(scientific name) (293)+TX, Eretmocerus eremicus (alternative name)(300)+TX, Helicoverpa zea NPV (alternative name) (431)+TX,Heterorhabditis bacteriophora and H. megidis (alternative name)(433)+TX, Hippodamia convergens (alternative name) (442)+TX, Leptomastixdactylopii (alternative name) (488)+TX, Macrolophus caliginosus(alternative name) (491)+TX, Mamestra brassicae NPV (alternative name)(494)+TX, Metaphycus helvolus (alternative name) (522)+TX, Metarhiziumanisopliae var. acridum (scientific name) (523)+TX, Metarhiziumanisopliae var. anisopliae (scientific name) (523)+TX, Neodiprionsertifer NPV and N. lecontei NPV (alternative name) (575)+TX, Orius spp.(alternative name) (596)+TX, Paecilomyces fumosoroseus (alternativename) (613)+TX, Phytoseiulus persimilis (alternative name) (644)+TX,Spodoptera exigua multicapsid nuclear polyhedrosis virus (scientificname) (741)+TX, Steinernema bibionis (alternative name) (742)+TX,Steinernema carpocapsae (alternative name) (742)+TX, Steinernema feltiae(alternative name) (742)+TX, Steinernema glaseri (alternative name)(742)+TX, Steinernema riobrave (alternative name) (742)+TX, Steinernemariobravis (alternative name) (742)+TX, Steinernema scapterisci(alternative name) (742)+TX, Steinernema spp. (alternative name)(742)+TX, Trichogramma spp. (alternative name) (826)+TX, Typhlodromusoccidentalis (alternative name) (844) and Verticillium lecanii(alternative name) (848)+TX, Bacillus subtilis var. amyloliquefaciensStrain FZB24 (available from Novozymes Biologicals Inc., 5400 CorporateCircle, Salem, Va. 24153, U.S.A. and known under the trade nameTaegro®)+TX,

a soil sterilant selected from the group of substances consisting ofiodomethane (IUPAC name) (542) and methyl bromide (537)+TX,

a chemosterilant selected from the group of substances consisting ofapholate [CCN]+TX, bisazir (alternative name) [CCN]+TX, busulfan(alternative name) [CCN]+TX, diflubenzuron (250)+TX, dimatif(alternative name) [CCN]+TX, hemel [CCN]+TX, hempa [CCN]+TX, metepa[CCN]+TX, methiotepa [CCN]+TX, methyl apholate [CCN]+TX, morzid[CCN]+TX, penfluron (alternative name) [CCN]+TX, tepa [CCN]+TX,thiohempa (alternative name) [CCN]+TX, thiotepa (alternative name)[CCN]+TX, tretamine (alternative name) [CCN] and uredepa (alternativename) [CCN]+TX,

an insect pheromone selected from the group of substances consisting of(E)-dec-5-en-1-yl acetate with (E)-dec-5-en-1-ol (IUPAC name) (222)+TX,(E)-tridec-4-en-1-yl acetate (IUPAC name) (829)+TX,(E)-6-methylhept-2-en-4-ol (IUPAC name) (541)+TX,(E,Z)-tetradeca-4,10-dien-1-yl acetate (IUPAC name) (779)+TX,(Z)-dodec-7-en-1-yl acetate (IUPAC name) (285)+TX, (Z)-hexadec-11-enal(IUPAC name) (436)+TX, (Z)-hexadec-11-en-1-yl acetate (IUPAC name)(437)+TX, (Z)-hexadec-13-en-11-yn-1-yl acetate (IUPAC name) (438)+TX,(Z)-icos-13-en-10-one (IUPAC name) (448)+TX, (Z)-tetradec-7-en-1-al(IUPAC name) (782)+TX, (Z)-tetradec-9-en-1-ol (IUPAC name) (783)+TX,(Z)-tetradec-9-en-1-yl acetate (IUPAC name) (784)+TX,(7E,9Z)-dodeca-7,9-dien-1-yl acetate (IUPAC name) (283)+TX,(9Z,11E)-tetradeca-9,11-dien-1-yl acetate (IUPAC name) (780)+TX,(9Z,12E)-tetradeca-9,12-dien-1-yl acetate (IUPAC name) (781)+TX,14-methyloctadec-1-ene (IUPAC name) (545)+TX, 4-methylnonan-5-ol with4-methylnonan-5-one (IUPAC name) (544)+TX, alpha-multistriatin(alternative name) [CCN]+TX, brevicomin (alternative name) [CCN]+TX,codlelure (alternative name) [CCN]+TX, codlemone (alternative name)(167)+TX, cuelure (alternative name) (179)+TX, disparlure (277)+TX,dodec-8-en-1-yl acetate (IUPAC name) (286)+TX, dodec-9-en-1-yl acetate(IUPAC name) (287)+TX, dodeca-8+TX, 10-dien-1-yl acetate (IUPAC name)(284)+TX, dominicalure (alternative name) [CCN]+TX, ethyl4-methyloctanoate (IUPAC name) (317)+TX, eugenol (alternative name)[CCN]+TX, frontalin (alternative name) [CCN]+TX, gossyplure (alternativename) (420)+TX, grandlure (421)+TX, grandlure I (alternative name)(421)+TX, grandlure II (alternative name) (421)+TX, grandlure III(alternative name) (421)+TX, grandlure IV (alternative name) (421)+TX,hexalure [CCN]+TX, ipsdienol (alternative name) [CCN]+TX, ipsenol(alternative name) [CCN]+TX, japonilure (alternative name) (481)+TX,lineatin (alternative name) [CCN]+TX, litlure (alternative name)[CCN]+TX, looplure (alternative name) [CCN]+TX, medlure [CCN]+TX,megatomoic acid (alternative name) [CCN]+TX, methyl eugenol (alternativename) (540)+TX, muscalure (563)+TX, octadeca-2,13-dien-1-yl acetate(IUPAC name) (588)+TX, octadeca-3,13-dien-1-yl acetate (IUPAC name)(589)+TX, orfralure (alternative name) [CCN]+TX, oryctalure (alternativename) (317)+TX, ostramone (alternative name) [CCN]+TX, siglure [CCN]+TX,sordidin (alternative name) (736)+TX, sulcatol (alternative name)[CCN]+TX, tetradec-11-en-1-yl acetate (IUPAC name) (785)+TX, trimedlure(839)+TX, trimedlure A (alternative name) (839)+TX, trimedlure B₁(alternative name) (839)+TX, trimedlure B₂ (alternative name) (839)+TX,trimedlure C (alternative name) (839) and trunc-call (alternative name)[CCN]+TX,

an insect repellent selected from the group of substances consisting of2-(octylthio)-ethanol (IUPAC name) (591)+TX, butopyronoxyl (933)+TX,butoxy(polypropylene glycol) (936)+TX, dibutyl adipate (IUPAC name)(1046)+TX, dibutyl phthalate (1047)+TX, dibutyl succinate (IUPAC name)(1048)+TX, diethyltoluamide [CCN]+TX, dimethyl carbate [CCN]+TX,dimethyl phthalate [CCN]+TX, ethyl hexanediol (1137)+TX, hexamide[CCN]+TX, methoquin-butyl (1276)+TX, methylneodecanamide [CCN]+TX,oxamate [CCN] and picaridin [CCN]+TX,

an insecticide selected from the group of substances consisting of1-dichloro-1-nitroethane (IUPAC/Chemical Abstracts name) (1058)+TX,1,1-dichloro-2,2-bis(4-ethylphenyl)ethane (IUPAC name) (1056), +TX,1,2-dichloropropane (IUPAC/Chemical Abstracts name) (1062)+TX,1,2-dichloropropane with 1,3-dichloropropene (IUPAC name) (1063)+TX,1-bromo-2-chloroethane (IUPAC/Chemical Abstracts name) (916)+TX,2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate (IUPAC name)(1451)+TX, 2,2-dichlorovinyl 2-ethylsulfinylethyl methyl phosphate(IUPAC name) (1066)+TX, 2-(1,3-dithiolan-2-yl)phenyl dimethylcarbamate(IUPAC/Chemical Abstracts name) (1109)+TX, 2-(2-butoxyethoxy)ethylthiocyanate (IUPAC/Chemical Abstracts name) (935)+TX,2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenyl methylcarbamate (IUPAC/ChemicalAbstracts name) (1084)+TX, 2-(4-chloro-3,5-xylyloxy)ethanol (IUPAC name)(986)+TX, 2-chlorovinyl diethyl phosphate (IUPAC name) (984)+TX,2-imidazolidone (IUPAC name) (1225)+TX, 2-isovalerylindan-1,3-dione(IUPAC name) (1246)+TX, 2-methyl(prop-2-ynyl)aminophenyl methylcarbamate(IUPAC name) (1284)+TX, 2-thiocyanatoethyl laurate (IUPAC name)(1433)+TX, 3-bromo-1-chloroprop-1-ene (IUPAC name) (917)+TX,3-methyl-1-phenylpyrazol-5-yl dimethylcarbamate (IUPAC name) (1283)+TX,4-methyl(prop-2-ynyl)amino-3,5-xylyl methylcarbamate (IUPAC name)(1285)+TX, 5,5-dimethyl-3-oxocyclohex-1-enyl dimethylcarbamate (IUPACname) (1085)+TX, abamectin (1)+TX, acephate (2)+TX, acetamiprid (4)+TX,acethion (alternative name) [CCN]+TX, acetoprole [CCN]+TX, acrinathrin(9)+TX, acrylonitrile (IUPAC name) (861)+TX, alanycarb (15)+TX, aldicarb(16)+TX, aldoxycarb (863)+TX, aldrin (864)+TX, allethrin (17)+TX,allosamidin (alternative name) [CCN]+TX, allyxycarb (866)+TX,alpha-cypermethrin (202)+TX, alpha-ecdysone (alternative name) [CCN]+TX,aluminium phosphide (640)+TX, amidithion (870)+TX, amidothioate(872)+TX, aminocarb (873)+TX, amiton (875)+TX, amiton hydrogen oxalate(875)+TX, amitraz (24)+TX, anabasine (877)+TX, athidathion (883)+TX, AVI382 (compound code)+TX, AZ 60541 (compound code)+TX, azadirachtin(alternative name) (41)+TX, azamethiphos (42)+TX, azinphos-ethyl(44)+TX, azinphos-methyl (45)+TX, azothoate (889)+TX, Bacillusthuringiensis delta endotoxins (alternative name) (52)+TX, bariumhexafluorosilicate (alternative name) [CCN]+TX, barium polysulfide(IUPAC/Chemical Abstracts name) (892)+TX, barthrin [CCN]+TX, Bayer22/190 (development code) (893)+TX, Bayer 22408 (development code)(894)+TX, bendiocarb (58)+TX, benfuracarb (60)+TX, bensultap (66)+TX,beta-cyfluthrin (194)+TX, beta-cypermethrin (203)+TX, bifenthrin(76)+TX, bioallethrin (78)+TX, bioallethrin S-cyclopentenyl isomer(alternative name) (79)+TX, bioethanomethrin [CCN]+TX, biopermethrin(908)+TX, bioresmethrin (80)+TX, bis(2-chloroethyl) ether (IUPAC name)(909)+TX, bistrifluron (83)+TX, borax (86)+TX, brofenvalerate(alternative name)+TX, bromfenvinfos (914)+TX, bromocyclen (918)+TX,bromo-DDT (alternative name) [CCN]+TX, bromophos (920)+TX,bromophos-ethyl (921)+TX, bufencarb (924)+TX, buprofezin (99)+TX,butacarb (926)+TX, butathiofos (927)+TX, butocarboxim (103)+TX, butonate(932)+TX, butoxycarboxim (104)+TX, butylpyridaben (alternative name)+TX,cadusafos (109)+TX, calcium arsenate [CCN]+TX, calcium cyanide (444)+TX,calcium polysulfide (IUPAC name) (111)+TX, camphechlor (941)+TX,carbanolate (943)+TX, carbaryl (115)+TX, carbofuran (118)+TX, carbondisulfide (IUPAC/Chemical Abstracts name) (945)+TX, carbon tetrachloride(IUPAC name) (946)+TX, carbophenothion (947)+TX, carbosulfan (119)+TX,cartap (123)+TX, cartap hydrochloride (123)+TX, cevadine (alternativename) (725)+TX, chlorbicyclen (960)+TX, chlordane (128)+TX, chlordecone(963)+TX, chlordimeform (964)+TX, chlordimeform hydrochloride (964)+TX,chlorethoxyfos (129)+TX, chlorfenapyr (130)+TX, chlorfenvinphos(131)+TX, chlorfluazuron (132)+TX, chlormephos (136)+TX, chloroform[CCN]+TX, chloropicrin (141)+TX, chlorphoxim (989)+TX, chlorprazophos(990)+TX, chlorpyrifos (145)+TX, chlorpyrifos-methyl (146)+TX,chlorthiophos (994)+TX, chromafenozide (150)+TX, cinerin I (696)+TX,cinerin II (696)+TX, cinerins (696)+TX, cis-resmethrin (alternativename)+TX, cismethrin (80)+TX, clocythrin (alternative name)+TX,cloethocarb (999)+TX, closantel (alternative name) [CCN]+TX,clothianidin (165)+TX, copper acetoarsenite [CCN]+TX, copper arsenate[CCN]+TX, copper oleate [CCN]+TX, coumaphos (174)+TX, coumithoate(1006)+TX, crotamiton (alternative name) [CCN]+TX, crotoxyphos(1010)+TX, crufomate (1011)+TX, cryolite (alternative name) (177)+TX, CS708 (development code) (1012)+TX, cyanofenphos (1019)+TX, cyanophos(184)+TX, cyanthoate (1020)+TX, cyclethrin [CCN]+TX, cycloprothrin(188)+TX, cyfluthrin (193)+TX, cyhalothrin (196)+TX, cypermethrin(201)+TX, cyphenothrin (206)+TX, cyromazine (209)+TX, cythioate(alternative name) [CCN]+TX, d-limonene (alternative name) [CCN]+TX,d-tetramethrin (alternative name) (788)+TX, DAEP (1031)+TX, dazomet(216)+TX, DDT (219)+TX, decarbofuran (1034)+TX, deltamethrin (223)+TX,demephion (1037)+TX, demephion-O (1037)+TX, demephion-S(1037)+TX,demeton (1038)+TX, demeton-methyl (224)+TX, demeton-O (1038)+TX,demeton-O-methyl (224)+TX, demeton-S(1038)+TX, demeton-S-methyl(224)+TX, demeton-S-methylsulphon (1039)+TX, diafenthiuron (226)+TX,dialifos (1042)+TX, diamidafos (1044)+TX, diazinon (227)+TX, dicapthon(1050)+TX, dichlofenthion (1051)+TX, dichlorvos (236)+TX, dicliphos(alternative name)+TX, dicresyl (alternative name) [CCN]+TX, dicrotophos(243)+TX, dicyclanil (244)+TX, dieldrin (1070)+TX, diethyl5-methylpyrazol-3-yl phosphate (IUPAC name) (1076)+TX, diflubenzuron(250)+TX, dilor (alternative name) [CCN]+TX, dimefluthrin [CCN]+TX,dimefox (1081)+TX, dimetan (1085)+TX, dimethoate (262)+TX, dimethrin(1083)+TX, dimethylvinphos (265)+TX, dimetilan (1086)+TX, dinex(1089)+TX, dinex-diclexine (1089)+TX, dinoprop (1093)+TX, dinosam(1094)+TX, dinoseb (1095)+TX, dinotefuran (271)+TX, diofenolan(1099)+TX, dioxabenzofos (1100)+TX, dioxacarb (1101)+TX, dioxathion(1102)+TX, disulfoton (278)+TX, dithicrofos (1108)+TX, DNOC (282)+TX,doramectin (alternative name) [CCN]+TX, DSP (1115)+TX, ecdysterone(alternative name) [CCN]+TX, El 1642 (development code) (1118)+TX,emamectin (291)+TX, emamectin benzoate (291)+TX, EMPC (1120)+TX,empenthrin (292)+TX, endosulfan (294)+TX, endothion (1121)+TX, endrin(1122)+TX, EPBP (1123)+TX, EPN (297)+TX, epofenonane (1124)+TX,eprinomectin (alternative name) [CCN]+TX, esfenvalerate (302)+TX,etaphos (alternative name) [CCN]+TX, ethiofencarb (308)+TX, ethion(309)+TX, ethiprole (310)+TX, ethoate-methyl (1134)+TX, ethoprophos(312)+TX, ethyl formate (IUPAC name) [CCN]+TX, ethyl-DDD (alternativename) (1056)+TX, ethylene dibromide (316)+TX, ethylene dichloride(chemical name) (1136)+TX, ethylene oxide [CCN]+TX, etofenprox (319)+TX,etrimfos (1142)+TX, EXD (1143)+TX, famphur (323)+TX, fenamiphos(326)+TX, fenazaflor (1147)+TX, fenchlorphos (1148)+TX, fenethacarb(1149)+TX, fenfluthrin (1150)+TX, fenitrothion (335)+TX, fenobucarb(336)+TX, fenoxacrim (1153)+TX, fenoxycarb (340)+TX, fenpirithrin(1155)+TX, fenpropathrin (342)+TX, fenpyrad (alternative name)+TX,fensulfothion (1158)+TX, fenthion (346)+TX, fenthion-ethyl [CCN]+TX,fenvalerate (349)+TX, fipronil (354)+TX, flonicamid (358)+TX,flubendiamide (CAS. Reg. No.: 272451-65-7)+TX, flucofuron (1168)+TX,flucycloxuron (366)+TX, flucythrinate (367)+TX, fluenetil (1169)+TX,flufenerim [CCN]+TX, flufenoxuron (370)+TX, flufenprox (1171)+TX,flumethrin (372)+TX, fluvalinate (1184)+TX, FMC 1137 (development code)(1185)+TX, fonofos (1191)+TX, formetanate (405)+TX, formetanatehydrochloride (405)+TX, formothion (1192)+TX, formparanate (1193)+TX,fosmethilan (1194)+TX, fospirate (1195)+TX, fosthiazate (408)+TX,fosthietan (1196)+TX, furathiocarb (412)+TX, furethrin (1200)+TX,gamma-cyhalothrin (197)+TX, gamma-HCH (430)+TX, guazatine (422)+TX,guazatine acetates (422)+TX, GY-81 (development code) (423)+TX,halfenprox (424)+TX, halofenozide (425)+TX, HCH (430)+TX, HEOD(1070)+TX, heptachlor (1211)+TX, heptenophos (432)+TX, heterophos[CCN]+TX, hexaflumuron (439)+TX, HHDN (864)+TX, hydramethylnon (443)+TX,hydrogen cyanide (444)+TX, hydroprene (445)+TX, hyquincarb (1223)+TX,imidacloprid (458)+TX, imiprothrin (460)+TX, indoxacarb (465)+TX,iodomethane (IUPAC name) (542)+TX, IPSP (1229)+TX, isazofos (1231)+TX,isobenzan (1232)+TX, isocarbophos (alternative name) (473)+TX, isodrin(1235)+TX, isofenphos (1236)+TX, isolane (1237)+TX, isoprocarb (472)+TX,isopropyl O-(methoxy-aminothiophosphoryl)salicylate (IUPAC name)(473)+TX, isoprothiolane (474)+TX, isothioate (1244)+TX, isoxathion(480)+TX, ivermectin (alternative name) [CCN]+TX, jasmolin I (696)+TX,jasmolin II (696)+TX, jodfenphos (1248)+TX, juvenile hormone I(alternative name) [CCN]+TX, juvenile hormone II (alternative name)[CCN]+TX, juvenile hormone III (alternative name) [CCN]+TX, kelevan(1249)+TX, kinoprene (484)+TX, lambda-cyhalothrin (198)+TX, leadarsenate [CCN]+TX, lepimectin (CCN)+TX, leptophos (1250)+TX, lindane(430)+TX, lirimfos (1251)+TX, lufenuron (490)+TX, lythidathion(1253)+TX, m-cumenyl methylcarbamate (IUPAC name) (1014)+TX, magnesiumphosphide (IUPAC name) (640)+TX, malathion (492)+TX, malonoben(1254)+TX, mazidox (1255)+TX, mecarbam (502)+TX, mecarphon (1258)+TX,menazon (1260)+TX, mephosfolan (1261)+TX, mercurous chloride (513)+TX,mesulfenfos (1263)+TX, metaflumizone (CCN)+TX, metam (519)+TX,metam-potassium (alternative name) (519)+TX, metam-sodium (519)+TX,methacrifos (1266)+TX, methamidophos (527)+TX, methanesulfonyl fluoride(IUPAC/Chemical Abstracts name) (1268)+TX, methidathion (529)+TX,methiocarb (530)+TX, methocrotophos (1273)+TX, methomyl (531)+TX,methoprene (532)+TX, methoquin-butyl (1276)+TX, methothrin (alternativename) (533)+TX, methoxychlor (534)+TX, methoxyfenozide (535)+TX, methylbromide (537)+TX, methyl isothiocyanate (543)+TX, methylchloroform(alternative name) [CCN]+TX, methylene chloride [CCN]+TX, metofluthrin[CCN]+TX, metolcarb (550)+TX, metoxadiazone (1288)+TX, mevinphos(556)+TX, mexacarbate (1290)+TX, milbemectin (557)+TX, milbemycin oxime(alternative name) [CCN]+TX, mipafox (1293)+TX, mirex (1294)+TX,monocrotophos (561)+TX, morphothion (1300)+TX, moxidectin (alternativename) [CCN]+TX, naftalofos (alternative name) [CCN]+TX, naled (567)+TX,naphthalene (IUPAC/Chemical Abstracts name) (1303)+TX, NC-170(development code) (1306)+TX, NC-184 (compound code)+TX, nicotine(578)+TX, nicotine sulfate (578)+TX, nifluridide (1309)+TX, nitenpyram(579)+TX, nithiazine (1311)+TX, nitrilacarb (1313)+TX, nitrilacarb 1:1zinc chloride complex (1313)+TX, NNI-0101 (compound code)+TX, NNI-0250(compound code)+TX, nornicotine (traditional name) (1319)+TX, novaluron(585)+TX, noviflumuron (586)+TX, O-5-dichloro-4-iodophenyl O-ethylethylphosphonothioate (IUPAC name) (1057)+TX, O,O-diethylO-4-methyl-2-oxo-2H-chromen-7-yl phosphorothioate (IUPAC name)(1074)+TX, O,O-diethyl O-6-methyl-2-propylpyrimidin-4-ylphosphorothioate (IUPAC name) (1075)+TX, O,O,O′,O′-tetrapropyldithiopyrophosphate (IUPAC name) (1424)+TX, oleic acid (IUPAC name)(593)+TX, omethoate (594)+TX, oxamyl (602)+TX, oxydemeton-methyl(609)+TX, oxydeprofos (1324)+TX, oxydisulfoton (1325)+TX, pp′-DDT(219)+TX, para-dichlorobenzene [CCN]+TX, parathion (615)+TX,parathion-methyl (616)+TX, penfluron (alternative name) [CCN]+TX,pentachlorophenol (623)+TX, pentachlorophenyl laurate (IUPAC name)(623)+TX, permethrin (626)+TX, petroleum oils (alternative name)(628)+TX, PH 60-38 (development code) (1328)+TX, phenkapton (1330)+TX,phenothrin (630)+TX, phenthoate (631)+TX, phorate (636)+TX, phosalone(637)+TX, phosfolan (1338)+TX, phosmet (638)+TX, phosnichlor (1339)+TX,phosphamidon (639)+TX, phosphine (IUPAC name) (640)+TX, phoxim (642)+TX,phoxim-methyl (1340)+TX, pirimetaphos (1344)+TX, pirimicarb (651)+TX,pirimiphos-ethyl (1345)+TX, pirimiphos-methyl (652)+TX,polychlorodicyclopentadiene isomers (IUPAC name) (1346)+TX,polychloroterpenes (traditional name) (1347)+TX, potassium arsenite[CCN]+TX, potassium thiocyanate [CCN]+TX, prallethrin (655)+TX,precocene I (alternative name) [CCN]+TX, precocene II (alternative name)[CCN]+TX, precocene III (alternative name) [CCN]+TX, primidophos(1349)+TX, profenofos (662)+TX, profluthrin [CCN]+TX, promacyl(1354)+TX, promecarb (1355)+TX, propaphos (1356)+TX, propetamphos(673)+TX, propoxur (678)+TX, prothidathion (1360)+TX, prothiofos(686)+TX, prothoate (1362)+TX, protrifenbute [CCN]+TX, pymetrozine(688)+TX, pyraclofos (689)+TX, pyrazophos (693)+TX, pyresmethrin(1367)+TX, pyrethrin I (696)+TX, pyrethrin II (696)+TX, pyrethrins(696)+TX, pyridaben (699)+TX, pyridalyl (700)+TX, pyridaphenthion(701)+TX, pyrimidifen (706)+TX, pyrimitate (1370)+TX, pyriproxyfen(708)+TX, quassia (alternative name) [CCN]+TX, quinalphos (711)+TX,quinalphos-methyl (1376)+TX, quinothion (1380)+TX, quintiofos (1381)+TX,R-1492 (development code) (1382)+TX, rafoxanide (alternative name)[CCN]+TX, resmethrin (719)+TX, rotenone (722)+TX, RU 15525 (developmentcode) (723)+TX, RU 25475 (development code) (1386)+TX, ryania(alternative name) (1387)+TX, ryanodine (traditional name) (1387)+TX,sabadilla (alternative name) (725)+TX, schradan (1389)+TX, sebufos(alternative name)+TX, selamectin (alternative name) [CCN]+TX, SI-0009(compound code)+TX, SI-0205 (compound code)+TX, SI-0404 (compoundcode)+TX, SI-0405 (compound code)+TX, silafluofen (728)+TX, SN 72129(development code) (1397)+TX, sodium arsenite [CCN]+TX, sodium cyanide(444)+TX, sodium fluoride (IUPAC/Chemical Abstracts name) (1399)+TX,sodium hexafluorosilicate (1400)+TX, sodium pentachlorophenoxide(623)+TX, sodium selenate (IUPAC name) (1401)+TX, sodium thiocyanate[CCN]+TX, sophamide (1402)+TX, spinosad (737)+TX, spiromesifen (739)+TX,spirotetrmat (CCN)+TX, sulcofuron (746)+TX, sulcofuron-sodium (746)+TX,sulfluramid (750)+TX, sulfotep (753)+TX, sulfuryl fluoride (756)+TX,sulprofos (1408)+TX, tar oils (alternative name) (758)+TX,tau-fluvalinate (398)+TX, tazimcarb (1412)+TX, TDE (1414)+TX,tebufenozide (762)+TX, tebufenpyrad (763)+TX, tebupirimfos (764)+TX,teflubenzuron (768)+TX, tefluthrin (769)+TX, temephos (770)+TX, TEPP(1417)+TX, terallethrin (1418)+TX, terbam (alternative name)+TX,terbufos (773)+TX, tetrachloroethane [CCN]+TX, tetrachlorvinphos(777)+TX, tetramethrin (787)+TX, theta-cypermethrin (204)+TX,thiacloprid (791)+TX, thiafenox (alternative name)+TX, thiamethoxam(792)+TX, thicrofos (1428)+TX, thiocarboxime (1431)+TX, thiocyclam(798)+TX, thiocyclam hydrogen oxalate (798)+TX, thiodicarb (799)+TX,thiofanox (800)+TX, thiometon (801)+TX, thionazin (1434)+TX, thiosultap(803)+TX, thiosultap-sodium (803)+TX, thuringiensin (alternative name)[CCN]+TX, tolfenpyrad (809)+TX, tralomethrin (812)+TX, transfluthrin(813)+TX, transpermethrin (1440)+TX, triamiphos (1441)+TX, triazamate(818)+TX, triazophos (820)+TX, triazuron (alternative name)+TX,trichlorfon (824)+TX, trichlormetaphos-3 (alternative name) [CCN]+TX,trichloronat (1452)+TX, trifenofos (1455)+TX, triflumuron (835)+TX,trimethacarb (840)+TX, triprene (1459)+TX, vamidothion (847)+TX,vaniliprole [CCN]+TX, veratridine (alternative name) (725)+TX, veratrine(alternative name) (725)+TX, XMC (853)+TX, xylylcarb (854)+TX, YI-5302(compound code)+TX, zeta-cypermethrin (205)+TX, zetamethrin (alternativename)+TX, zinc phosphide (640)+TX, zolaprofos (1469) and ZXI 8901(development code) (858)+TX, cyantraniliprole [736994-63-19+TX,chlorantraniliprole [500008-45-7]+TX, cyenopyrafen [560121-52-0]+TX,cyflumetofen [400882-07-7]+TX, pyrifluquinazon [337458-27-2]+TX,spinetoram [187166-40-1+187166-15-0]+TX, spirotetramat [203313-25-1]+TX,sulfoxaflor [946578-00-3]+TX, flufiprole [704886-18-0]+TX, meperfluthrin[915288-13-0]+TX, tetramethylfluthrin [84937-88-2]+TX, triflumezopyrim(disclosed in WO 2012/092115)+TX,

a molluscicide selected from the group of substances consisting ofbis(tributyltin) oxide (IUPAC name) (913)+TX, bromoacetamide [CCN]+TX,calcium arsenate [CCN]+TX, cloethocarb (999)+TX, copper acetoarsenite[CCN]+TX, copper sulfate (172)+TX, fentin (347)+TX, ferric phosphate(IUPAC name) (352)+TX, metaldehyde (518)+TX, methiocarb (530)+TX,niclosamide (576)+TX, niclosamide-olamine (576)+TX, pentachlorophenol(623)+TX, sodium pentachlorophenoxide (623)+TX, tazimcarb (1412)+TX,thiodicarb (799)+TX, tributyltin oxide (913)+TX, trifenmorph (1454)+TX,trimethacarb (840)+TX, triphenyltin acetate (IUPAC name) (347) andtriphenyltin hydroxide (IUPAC name) (347)+TX, pyriprole[394730-71-3]+TX,

a nematicide selected from the group of substances consisting ofAKD-3088 (compound code)+TX, 1,2-dibromo-3-chloropropane (IUPAC/ChemicalAbstracts name) (1045)+TX, 1,2-dichloropropane (IUPAC/Chemical Abstractsname) (1062)+TX, 1,2-dichloropropane with 1,3-dichloropropene (IUPACname) (1063)+TX, 1,3-dichloropropene (233)+TX,3,4-dichlorotetrahydrothiophene 1,1-dioxide (IUPAC/Chemical Abstractsname) (1065)+TX, 3-(4-chlorophenyl)-5-methylrhodanine (IUPAC name)(980)+TX, 5-methyl-6-thioxo-1,3,5-thiadiazinan-3-ylacetic acid (IUPACname) (1286)+TX, 6-isopentenylaminopurine (alternative name) (210)+TX,abamectin (1)+TX, acetoprole [CCN]+TX, alanycarb (15)+TX, aldicarb(16)+TX, aldoxycarb (863)+TX, AZ 60541 (compound code)+TX, benclothiaz[CCN]+TX, benomyl (62)+TX, butylpyridaben (alternative name)+TX, cadusathiazolidines fos (109)+TX, carbofuran (118)+TX, carbon disulfide(945)+TX, carbosulfan (119)+TX, chloropicrin (141)+TX, chlorpyrifos(145)+TX, cloethocarb (999)+TX, cytokinins (alternative name) (210)+TX,dazomet (216)+TX, DBCP (1045)+TX, DCIP (218)+TX, diamidafos (1044)+TX,dichlofenthion (1051)+TX, dicliphos (alternative name)+TX, dimethoate(262)+TX, doramectin (alternative name) [CCN]+TX, emamectin (291)+TX,emamectin benzoate (291)+TX, eprinomectin (alternative name) [CCN]+TX,ethoprophos (312)+TX, ethylene dibromide (316)+TX, fenamiphos (326)+TX,fenpyrad (alternative name)+TX, fensulfothion (1158)+TX, fosthiazate(408)+TX, fosthietan (1196)+TX, furfural (alternative name) [CCN]+TX,GY-81 (development code) (423)+TX, heterophos [CCN]+TX, iodomethane(IUPAC name) (542)+TX, isamidofos (1230)+TX, isazofos (1231)+TX,ivermectin (alternative name) [CCN]+TX, kinetin (alternative name)(210)+TX, mecarphon (1258)+TX, metam (519)+TX, metam-potassium(alternative name) (519)+TX, metam-sodium (519)+TX, methyl bromide(537)+TX, methyl isothiocyanate (543)+TX, milbemycin oxime (alternativename) [CCN]+TX, moxidectin (alternative name) [CCN]+TX, Myrotheciumverrucaria composition (alternative name) (565)+TX, NC-184 (compoundcode)+TX, oxamyl (602)+TX, phorate (636)+TX, phosphamidon (639)+TX,phosphocarb [CCN]+TX, sebufos (alternative name)+TX, selamectin(alternative name) [CCN]+TX, spinosad (737)+TX, terbam (alternativename)+TX, terbufos (773)+TX, tetrachlorothiophene (IUPAC/ChemicalAbstracts name) (1422)+TX, thiafenox (alternative name)+TX, thionazin(1434)+TX, triazophos (820)+TX, triazuron (alternative name)+TX,xylenols [CCN]+TX, YI-5302 (compound code) and zeatin (alternative name)(210)+TX, fluensulfone [318290-98-1]+TX,

a nitrification inhibitor selected from the group of substancesconsisting of potassium ethylxanthate [CCN] and nitrapyrin (580)+TX,

a plant activator selected from the group of substances consisting ofacibenzolar (6)+TX, acibenzolar-S-methyl (6)+TX, probenazole (658) andReynoutria sachalinensis extract (alternative name) (720)+TX,

a rodenticide selected from the group of substances consisting of2-isovalerylindan-1,3-dione (IUPAC name) (1246)+TX,4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748)+TX,alpha-chlorohydrin [CCN]+TX, aluminium phosphide (640)+TX, antu(880)+TX, arsenous oxide (882)+TX, barium carbonate (891)+TX,bisthiosemi (912)+TX, brodifacoum (89)+TX, bromadiolone (91)+TX,bromethalin (92)+TX, calcium cyanide (444)+TX, chloralose (127)+TX,chlorophacinone (140)+TX, cholecalciferol (alternative name) (850)+TX,coumachlor (1004)+TX, coumafuryl (1005)+TX, coumatetralyl (175)+TX,crimidine (1009)+TX, difenacoum (246)+TX, difethialone (249)+TX,diphacinone (273)+TX, ergocalciferol (301)+TX, flocoumafen (357)+TX,fluoroacetamide (379)+TX, flupropadine (1183)+TX, flupropadinehydrochloride (1183)+TX, gamma-HCH (430)+TX, HCH (430)+TX, hydrogencyanide (444)+TX, iodomethane (IUPAC name) (542)+TX, lindane (430)+TX,magnesium phosphide (IUPAC name) (640)+TX, methyl bromide (537)+TX,norbormide (1318)+TX, phosacetim (1336)+TX, phosphine (IUPAC name)(640)+TX, phosphorus [CCN]+TX, pindone (1341)+TX, potassium arsenite[CCN]+TX, pyrinuron (1371)+TX, scilliroside (1390)+TX, sodium arsenite[CCN]+TX, sodium cyanide (444)+TX, sodium fluoroacetate (735)+TX,strychnine (745)+TX, thallium sulfate [CCN]+TX, warfarin (851) and zincphosphide (640)+TX,

a synergist selected from the group of substances consisting of2-(2-butoxyethoxy)-ethyl piperonylate (IUPAC name) (934)+TX,5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone (IUPAC name) (903)+TX,farnesol with nerolidol (alternative name) (324)+TX, MB-599 (developmentcode) (498)+TX, MGK 264 (development code) (296)+TX, piperonyl butoxide(649)+TX, piprotal (1343)+TX, propyl isomer (1358)+TX, S421 (developmentcode) (724)+TX, sesamex (1393)+TX, sesasmolin (1394) and sulfoxide(1406)+TX,

an animal repellent selected from the group of substances consisting ofanthraquinone (32)+TX, chloralose (127)+TX, copper naphthenate [CCN]+TX,copper oxychloride (171)+TX, diazinon (227)+TX, dicyclopentadiene(chemical name) (1069)+TX, guazatine (422)+TX, guazatine acetates(422)+TX, methiocarb (530)+TX, pyridin-4-amine (IUPAC name) (23)+TX,thiram (804)+TX, trimethacarb (840)+TX, zinc naphthenate [CCN] and ziram(856)+TX,

a virucide selected from the group of substances consisting of imanin(alternative name) [CCN] and ribavirin (alternative name) [CCN]+TX,

a wound protectant selected from the group of substances consisting ofmercuric oxide (512)+TX, octhilinone (590) and thiophanate-methyl(802)+TX,

and biologically active compounds selected from the group consisting ofametoctradin [865318-97-4]+TX, amisulbrom [348635-87-0]+TX, azaconazole[60207-31-0]+TX, benzovindiflupyr [1072957-71-1]+TX, bitertanol[70585-36-3]+TX, bixafen [581809-46-3]+TX, bromuconazole[116255-48-2]+TX, coumoxystrobin [850881-70-8]+TX, cyproconazole[94361-06-5]+TX, difenoconazole [119446-68-3]+TX, diniconazole[83657-24-3]+TX, enoxastrobin [238410-11-2]+TX, epoxiconazole[106325-08-0]+TX, fenbuconazole [114369-43-6]+TX, fenpyrazamine[473798-59-3]+TX, fluquinconazole [136426-54-5]+TX, flusilazole[85509-19-9]+TX, flutriafol [76674-21-0]+TX, fluxapyroxad[907204-31-3]+TX, fluopyram [658066-35-4]+TX, fenaminstrobin[366815-39-6]+TX, isofetamid [875915-78-9]+TX, hexaconazole[79983-71-4]+TX, imazalil [35554-44-0]+TX, imibenconazole[86598-92-7]+TX, ipconazole [125225-28-7]+TX, ipfentrifluconazole[1417782-08-1]+TX, isotianil [224049-04-1]+TX, mandestrobin[173662-97-0] (can be prepared according to the procedures described inWO 2010/093059)+TX, mefentrifluconazole [1417782-03-6]+TX, metconazole[125116-23-6]+TX, myclobutanil [88671-89-0]+TX, paclobutrazol[76738-62-0]+TX, pefurazoate [101903-30-4]+TX, penflufen[494793-67-8]+TX, penconazole [66246-88-6]+TX, prothioconazole[178928-70-6]+TX, pyrifenox [88283-41-4]+TX, prochloraz [67747-09-5]+TX,propiconazole [60207-90-1]+TX, simeconazole [149508-90-7]+TX,tebuconazole [107534-96-3]+TX, tetraconazole [112281-77-3]+TX,triadimefon [43121-43-3]+TX, triadimenol [55219-65-3]+TX, triflumizole[99387-89-0]+TX, triticonazole [131983-72-7]+TX, ancymidol[12771-68-5]+TX, fenarimol [60168-88-9]+TX, nuarimol [63284-71-9]+TX,bupirimate [41483-43-6]+TX, dimethirimol [5221-53-4]+TX, ethirimol[23947-60-6]+TX, dodemorph [1593-77-7]+TX, fenpropidin [67306-00-7]+TX,fenpropimorph [67564-91-4]+TX, spiroxamine [118134-30-8]+TX, tridemorph[81412-43-3]+TX, cyprodinil [121552-61-2]+TX, mepanipyrim[110235-47-7]+TX, pyrimethanil [53112-28-0]+TX, fenpiclonil[74738-17-3]+TX, fludioxonil [131341-86-1]+TX, fluindapyr[1383809-87-7]+TX, benalaxyl [71626-11-4]+TX, furalaxyl [57646-30-7]+TX,metalaxyl [57837-19-1]+TX, R-metalaxyl [70630-17-0]+TX, ofurace[58810-48-3]+TX, oxadixyl [77732-09-3]+TX, benomyl [17804-35-2]+TX,carbendazim [10605-21-7]+TX, debacarb [62732-91-6]+TX, fuberidazole[3878-19-1]+TX, thiabendazole [148-79-8]+TX, chlozolinate[84332-86-5]+TX, dichlozoline [24201-58-9]+TX, iprodione[36734-19-7]+TX, myclozoline [54864-61-8]+TX, procymidone[32809-16-8]+TX, vinclozoline [50471-44-8]+TX, boscalid[188425-85-6]+TX, carboxin [5234-68-4]+TX, fenfuram [24691-80-3]+TX,flutolanil [66332-96-5]+TX, flutianil [958647-10-4]+TX, mepronil[55814-41-0]+TX, oxycarboxin [5259-88-1]+TX, penthiopyrad[183675-82-3]+TX, thifluzamide [130000-40-7]+TX, guazatine[108173-90-6]+TX, dodine [2439-10-3] [112-65-2] (free base)+TX,iminoctadine [13516-27-3]+TX, azoxystrobin [131860-33-8]+TX,dimoxystrobin [149961-52-4]+TX, enestroburin {Proc. BCPC, Int. Congr.,Glasgow, 2003, 1, 93}+TX, fluoxastrobin [361377-29-9]+TX,kresoxim-methyl [143390-89-0]+TX, metominostrobin [133408-50-1]+TX,trifloxystrobin [141517-21-7]+TX, orysastrobin [248593-16-0]+TX,picoxystrobin [117428-22-5]+TX, pyraclostrobin [175013-18-0]+TX,pyraoxystrobin [862588-11-2]+TX, ferbam [14484-64-1]+TX, mancozeb[8018-01-7]+TX, maneb [12427-38-2]+TX, metiram [9006-42-2]+TX, propineb[12071-83-9]+TX, thiram [137-26-8]+TX, zineb [12122-67-7]+TX, ziram[137-30-4]+TX, captafol [2425-06-1]+TX, captan [133-06-2]+TX,dichlofluanid [1085-98-9]+TX, fluoroimide [41205-21-4]+TX, folpet[133-07-3]+TX, tolylfluanid [731-27-1]+TX, bordeaux mixture[8011-63-0]+TX, copperhydroxid [20427-59-2]+TX, copperoxychlorid[1332-40-7]+TX, coppersulfat [7758-98-7]+TX, copperoxid [1317-39-1]+TX,mancopper [53988-93-5]+TX, oxine-copper [10380-28-6]+TX, dinocap[131-72-6]+TX, nitrothal-isopropyl [10552-74-6]+TX, edifenphos[17109-49-8]+TX, iprobenphos [26087-47-8]+TX, isoprothiolane[50512-35-1]+TX, phosdiphen [36519-00-3]+TX, pyrazophos [13457-18-6]+TX,tolclofos-methyl [57018-04-9]+TX, acibenzolar-S-methyl [135158-54-2]+TX,anilazine [101-05-3]+TX, benthiavalicarb [413615-35-7]+TX, blasticidin-S[2079-00-7]+TX, chinomethionat [2439-01-2]+TX, chloroneb [2675-77-6]+TX,chlorothalonil [1897-45-6]+TX, cyflufenamid [180409-60-3]+TX, cymoxanil[57966-95-7]+TX, dichlone [117-80-6]+TX, diclocymet [139920-32-4]+TX,diclomezine [62865-36-5]+TX, dicloran [99-30-9]+TX, diethofencarb[87130-20-9]+TX, dimethomorph [110488-70-5]+TX, SYP-L190 (Flumorph)[211867-47-9]+TX, dithianon [3347-22-6]+TX, ethaboxam [162650-77-3]+TX,etridiazole [2593-15-9]+TX, famoxadone [131807-57-3]+TX, fenamidone[161326-34-7]+TX, fenoxanil [115852-48-7]+TX, fentin [668-34-8]+TX,ferimzone [89269-64-7]+TX, fluazinam [79622-59-6]+TX, fluopicolide[239110-15-7]+TX, flusulfamide [106917-52-6]+TX, fenhexamid[126833-17-8]+TX, fosetyl-aluminium [39148-24-8]+TX, hymexazol[10004-44-1]+TX, iprovalicarb [140923-17-7]+TX, IKF-916 (Cyazofamid)[120116-88-3]+TX, kasugamycin [6980-18-3]+TX, methasulfocarb[66952-49-6]+TX, metrafenone [220899-03-6]+TX, pencycuron[66063-05-6]+TX, phthalide [27355-22-2]+TX, picarbutrazox[500207-04-5]+TX, polyoxins [11113-80-7]+TX, probenazole[27605-76-1]+TX, propamocarb [25606-41-1]+TX, proquinazid[189278-12-4]+TX, pydiflumetofen [1228284-64-7]+TX, pyrametostrobin[915410-70-7]+TX, pyroquilon [57369-32-1]+TX, pyriofenone[688046-61-9]+TX, pyribencarb [799247-52-2]+TX, pyrisoxazole[847749-37-5]+TX, quinoxyfen [124495-18-7]+TX, quintozene [82-68-8]+TX,sulfur [7704-34-9]+TX, Timorex Gold′ (plant extract containing tea treeoil from the Stockton Group)+TX, tebufloquin [376645-78-2]+TX, tiadinil[223580-51-6]+TX, triazoxide [72459-58-6]+TX, tolprocarb[911499-62-2]+TX, triclopyricarb [902760-40-1]+TX, tricyclazole[41814-78-2]+TX, triforine [26644-46-2]+TX, validamycin [37248-47-8]+TX,valifenalate [283159-90-0]+TX, zoxamide (RH7281) [156052-68-5]+TX,mandipropamid [374726-62-2]+TX, isopyrazam [881685-58-1]+TX,phenamacril+TX, sedaxane [874967-67-6]+TX, trinexapac-ethyl[95266-40-3]+TX, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid(9-dichloromethylene-1,2,3,4-tetrahydro-1,4-methano-naphthalen-5-yl)-amide(disclosed in WO 2007/048556)+TX,3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid(3′,4′,5′-trifluoro-biphenyl-2-yl)-amide (disclosed in WO2006/087343)+TX,[(3S,4R,4aR,6S,6aS,12R,12aS,12bS)-3-[(cyclopropylcarbonyl)oxy]-1,3,4,4a,5,6,6a,12,12a,12b-decahydro-6,12-dihydroxy-4,6a,12b-trimethyl-11-oxo-9-(3-pyridinyl)-2H,11Hnaphtho[2,1-b]pyrano[3,4-e]pyran-4-yl]methyl-cyclopropanecarboxylate[915972-17-7]+TX and1,3,5-trimethyl-N-(2-methyl-1-oxopropyl)-N-[3-(2-methylpropyl)-4-[2,2,2-trifluoro-1-methoxy-1-(trifluoromethyl)ethyl]phenyl]-1H-pyrazole-4-carboxamide[926914-55-8]+TX,

or a biologically active compound selected from the group consisting ofN-[(5-chloro-2-isopropyl-phenyl)methyl]-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-pyrazole-4-carboxamide(can be prepared according to the procedures described in WO2010/130767)+TX,2,6-Dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c′]dipyrrole-1,3,5,7(2H,6H)-tetrone(can be prepared according to the procedures described in WO2011/138281)+TX,6-ethyl-5,7-dioxo-pyrrolo[4,5][1,4]dithiino[1,2-c]isothiazole-3-carbonitrile+TX,4-(2-bromo-4-fluoro-phenyl)-N-(2-chloro-6-fluoro-phenyl)-2,5-dimethyl-pyrazol-3-amine(can be prepared according to the procedures described in WO2012/031061)+TX,3-(difluoromethyl)-N-(7-fluoro-1,1,3-trimethyl-indan-4-yl)-1-methyl-pyrazole-4-carboxamide(can be prepared according to the procedures described in WO2012/084812)+TX, CAS 850881-30-0+TX,3-(3,4-dichloro-1,2-thiazol-5-ylmethoxy)-1,2-benzothiazole 1,1-dioxide(can be prepared according to the procedures described in WO2007/129454)+TX,2-[2-[(2,5-dimethylphenoxy)methyl]phenyl]-2-methoxy-N-methyl-acetamide+TX,3-(4,4-difluoro-3,4-dihydro-3,3-dimethylisoquinolin-1-yl)quinolone (canbe prepared according to the procedures described in WO 2005/070917)+TX,2-[2-fluoro-6-[(8-fluoro-2-methyl-3-quinolyl)oxy]phenyl]propan-2-ol (canbe prepared according to the procedures described in WO 2011/081174)+TX,2-[2-[(7,8-difluoro-2-methyl-3-quinolyl)oxy]-6-fluoro-phenyl]propan-2-ol(can be prepared according to the procedures described in WO2011/081174)+TX, oxathiapiprolin+TX [1003318-67-9], tert-butylN-[6-[[[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate+TX,N-[2-(3,4-difluorophenyl)phenyl]-3-(trifluoromethyl)pyrazine-2-carboxamide(can be prepared according to the procedures described in WO2007/072999)+TX,3-(difluoromethyl)-1-methyl-N-[(3R)-1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide(can be prepared according to the procedures described in WO2014/013842)+TX, 2,2,2-trifluoroethylN-[2-methyl-1-[[(4-methylbenzoyl)amino]methyl]propyl]carbamate+TX,(2RS)-2-[4-(4-chlorophenoxy)-α,α,α-trifluoro-o-tolyl]-1-(1H-1,2,4-triazol-1-yl)propan-2-ol+TX,(2RS)-2-[4-(4-chlorophenoxy)-α,α,α-trifluoro-o-tolyl]-3-methyl-1-(1H-1,2,4-triazol-1-yl)butan-2-ol+TX,2-(difluoromethyl)-N-[(3R)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide+TX,2-(difluoromethyl)-N-[3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide+TX,N′-(2,5-dimethyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine+TX,N′-[4-(4,5-dichlorothiazol-2-yl)oxy-2,5-dimethyl-phenyl]-N-ethyl-N-methyl-formamidine(can be prepared according to the procedures described in WO2007/031513)+TX,[2-[3-[2-[1-[2-[3,5-bis(difluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]thiazol-4-yl]-4,5-dihydroisoxazol-5-yl]-3-chloro-phenyl]methanesulfonate (can be prepared according to the procedures describedin WO 2012/025557)+TX, but-3-ynylN-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate(can be prepared according to the procedures described in WO2010/000841)+TX,2-[[3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl]-4H-1,2,4-triazole-3-thione(can be prepared according to the procedures described in WO2010/146031)+TX, methylN-[[5-[4-(2,4-dimethylphenyl)triazol-2-yl]-2-methyl-phenyl]methyl]carbamate+TX,3-chloro-6-methyl-5-phenyl-4-(2,4,6-trifluorophenyl)pyridazine (can beprepared according to the procedures described in WO 2005/121104)+TX,2-[2-chloro-4-(4-chlorophenoxy)phenyl]-1-(1,2,4-triazol-1-yl)propan-2-ol(can be prepared according to the procedures described in WO2013/024082)+TX,3-chloro-4-(2,6-difluorophenyl)-6-methyl-5-phenyl-pyridazine (can beprepared according to the procedures described in WO 2012/020774)+TX,4-(2,6-difluorophenyl)-6-methyl-5-phenyl-pyridazine-3-carbonitrile (canbe prepared according to the procedures described in WO 2012/020774)+TX,(R)-3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide(can be prepared according to the procedures described in WO2011/162397)+TX,3-(difluoromethyl)-N-(7-fluoro-1,1,3-trimethyl-indan-4-yl)-1-methyl-pyrazole-4-carboxamide(can be prepared according to the procedures described in WO2012/084812)+TX,1-[2-[[1-(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methyl-phenyl]-4-methyl-tetrazol-5-one(can be prepared according to the procedures described in WO2013/162072)+TX,1-methyl-4-[3-methyl-2-[[2-methyl-4-(3,4,5-trimethylpyrazol-1-yl)phenoxy]methyl]phenyl]tetrazol-5-one(can be prepared according to the procedures described in WO2014/051165)+TX,(Z,2E)-5-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide+TX,(4-phenoxyphenyl)methyl 2-amino-6-methyl-pyridine-3-carboxylate+TX,N-(5-chloro-2-isopropylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methylpyrazole-4-carboxamide[1255734-28-1] (can be prepared according to the procedures described inWO 2010/130767)+TX,3-(difluoromethyl)-N-[(R)-2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl]-1-methylpyrazole-4-carboxamide[1352994-67-2]+TX,N′-(2,5-dimethyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine+TX,N′-[4-(4,5-dichloro-thiazol-2-yloxy)-2,5-dimethyl-phenyl]-N-ethyl-N-methyl-formamidine+TX,N′-(2,5-dimethyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine+TX,N′-[4-(4,5-dichloro-thiazol-2-yloxy)-2,5-dimethyl-phenyl]-N-ethyl-N-methyl-formamidine+TX,

(fenpicoxamid [517875-34-2] (as described in WO 2003/035617))+TX,(1S)-2,2-bis(4-fluorophenyl)-1-methylethylN-{[3-(acetyloxy)-4-methoxy-2-pyridyl]carbonyl}-L-alaninate[1961312-55-9] (as described in WO 2016/122802)+TX,2-(difluoromethyl)-N-(1,1,3-trimethylindan-4-yl)pyridine-3-carboxamide+TX,2-(difluoromethyl)-N-(3-ethyl-1,1-dimethyl-indan-4-yl)pyridine-3-carboxamide+TX,2-(difluoromethyl)-N-(1,1-dimethyl-3-propyl-indan-4-yl)pyridine-3-carboxamide+TX,2-(difluoromethyl)-N-(3-isobutyl-1,1-dimethyl-indan-4-yl)pyridine-3-carboxamide+TX,2-(difluoromethyl)-N-[(3R)-1,1,3-trimethylindan-4-yl]pyridine-3-carboxamide+TX,2-(difluoromethyl)-N-[(3R)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide+TX,and2-(difluoromethyl)-N-[(3R)-1,1-dimethyl-3-propyl-indan-4-yl]pyridine-3-carboxamide+TX,wherein each of these carboxamide compounds can be prepared according tothe procedures described in WO 2014/095675 and/or WO 2016/139189.

The references in brackets behind the active ingredients, e.g.[3878-19-1] refer to the Chemical Abstracts Registry number. The abovedescribed mixing partners are known. Where the active ingredients areincluded in “The Pesticide Manual” [The Pesticide Manual-A WorldCompendium; Thirteenth Edition; Editor: C. D. S. TomLin; The BritishCrop Protection Council], they are described therein under the entrynumber given in round brackets hereinabove for the particular compound;for example, the compound “abamectin” is described under entry number(1). Where “[CCN]” is added hereinabove to the particular compound, thecompound in question is included in the “Compendium of Pesticide CommonNames”, which is accessible on the internet [A. Wood; Compendium ofPesticide Common Names, Copyright © 1995-2004]; for example, thecompound “acetoprole” is described under the internet addresshttp://www.alanwood.net/pesticides/acetoprole.html.

Most of the active ingredients described above are referred tohereinabove by a so-called “common name”, the relevant “ISO common name”or another “common name” being used in individual cases. If thedesignation is not a “common name”, the nature of the designation usedinstead is given in round brackets for the particular compound; in thatcase, the IUPAC name, the IUPAC/Chemical Abstracts name, a “chemicalname”, a “traditional name”, a “compound name” or a “develoment code” isused or, if neither one of those designations nor a “common name” isused, an “alternative name” is employed. “CAS Reg. No” means theChemical Abstracts Registry Number.

The active ingredient mixture of the compounds of formula (I) selectedfrom one compound as represented in Tables A1 to A8 or Table B1 to B8(above) or Table E or Table F or Table G (below) is preferably in amixing ratio of from 100:1 to 1:6000, especially from 50:1 to 1:50, moreespecially in a ratio of from 20:1 to 1:20, even more especially from10:1 to 1:10, very especially from 5:1 and 1:5, special preference beinggiven to a ratio of from 2:1 to 1:2, and a ratio of from 4:1 to 2:1being likewise preferred, above all in a ratio of 1:1, or 5:1, or 5:2,or 5:3, or 5:4, or 4:1, or 4:2, or 4:3, or 3:1, or 3:2, or 2:1, or 1:5,or 2:5, or 3:5, or 4:5, or 1:4, or 2:4, or 3:4, or 1:3, or 2:3, or 1:2,or 1:600, or 1:300, or 1:150, or 1:35, or 2:35, or 4:35, or 1:75, or2:75, or 4:75, or 1:6000, or 1:3000, or 1:1500, or 1:350, or 2:350, or4:350, or 1:750, or 2:750, or 4:750. Those mixing ratios are by weight.

The mixtures as described above can be used in a method for controllingpests, which comprises applying a composition comprising a mixture asdescribed above to the pests or their environment, with the exception ofa method for treatment of the human or animal body by surgery or therapyand diagnostic methods practised on the human or animal body.

The mixtures comprising a compound as represented in Tables A1 to A8 orTable B1 to B8 (above) or Table E or Table F or Table G (below), and oneor more active ingredients as described above can be applied, forexample, in a single “ready-mix” form, in a combined spray mixturecomposed from separate formulations of the single active ingredientcomponents, such as a “tank-mix”, and in a combined use of the singleactive ingredients when applied in a sequential manner, i.e. one afterthe other with a reasonably short period, such as a few hours or days.The order of applying a compound as represented Tables A1 to A8 or TableB1 to B8 (above) or Table E or Table F or Table G (below) and the activeingredient(s) as described above, is not essential for working thepresent invention.

The compositions according to the invention can also comprise furthersolid or liquid auxiliaries, such as stabilizers, for exampleunepoxidized or epoxidized vegetable oils (for example epoxidizedcoconut oil, rapeseed oil or soya oil), antifoams, for example siliconeoil, preservatives, viscosity regulators, binders and/or tackifiers,fertilizers or other active ingredients for achieving specific effects,for example bactericides, fungicides, nematocides, plant activators,molluscicides or herbicides.

The compositions according to the invention are prepared in a mannerknown per se, in the absence of auxiliaries for example by grinding,screening and/or compressing a solid active ingredient and in thepresence of at least one auxiliary for example by intimately mixingand/or grinding the active ingredient with the auxiliary (auxiliaries).These processes for the preparation of the compositions and the use ofthe compounds (I) for the preparation of these compositions are also asubject of the invention.

Another aspect of the invention is related to the use of a compound ofFormula (I) or of a preferred individual compound as defined herein, ofa composition comprising at least one compound of Formula (I) or atleast one preferred individual compound as above-defined, or of afungicidal or insecticidal mixture comprising at least one compound ofFormula (I) or at least one preferred individual compound asabove-defined, in admixture with other fungicides or insecticides asdescribed above, for controlling or preventing infestation of plants,e.g. useful plants such as crop plants, propagation material thereof,e.g. seeds, harvested crops, e.g. harvested food crops, or non-livingmaterials by insects or by phytopathogenic microorganisms, preferablyfungal organisms.

A further aspect of invention is related to a method of controlling orpreventing an infestation of plants, e.g. useful plants such as cropplants, propagation material thereof, e.g. seeds, harvested crops, e.g.harvested food crops, or of non-living materials by phytopathogenic orspoilage microorganisms or organisms potentially harmful to man,especially fungal organisms, which comprises the application of acompound of formula (I) or of a preferred individual compound asabove-defined as active ingredient to the plants, to parts of the plantsor to the locus thereof, to the propagation material thereof, or to anypart of the non-living materials.

Controlling or preventing means reducing infestation by insects or byphytopathogenic or spoilage microorganisms or organisms potentiallyharmful to man, especially fungal organisms, to such a level that animprovement is demonstrated.

A preferred method of controlling or preventing an infestation of cropplants by phytopathogenic microorganisms, especially fungal organisms,or insects which comprises the application of a compound of formula (I),or an agrochemical composition which contains at least one of saidcompounds, is foliar application. The frequency of application and therate of application will depend on the risk of infestation by thecorresponding pathogen or insect. However, the compounds of formula (I)can also penetrate the plant through the roots via the soil (systemicaction) by drenching the locus of the plant with a liquid formulation,or by applying the compounds in solid form to the soil, e.g. in granularform (soil application). In crops of water rice such granulates can beapplied to the flooded rice field. The compounds of formula (I) may alsobe applied to seeds (coating) by impregnating the seeds or tubers eitherwith a liquid formulation of the fungicide or coating them with a solidformulation.

A formulation, e.g. a composition containing the compound of formula(I), and, if desired, a solid or liquid adjuvant or monomers forencapsulating the compound of formula (I), may be prepared in a knownmanner, typically by intimately mixing and/or grinding the compound withextenders, for example solvents, solid carriers and, optionally, surfaceactive compounds (surfactants).

The application methods for the compositions, that is the methods ofcontrolling pests of the abovementioned type, such as spraying,atomizing, dusting, brushing on, dressing, scattering or pouring—whichare to be selected to suit the intended aims of the prevailingcircumstances—and the use of the compositions for controlling pests ofthe abovementioned type are other subjects of the invention. Typicalrates of concentration are between 0.1 and 1000 ppm, preferably between0.1 and 500 ppm, of active ingredient. The rate of application perhectare is preferably 1 g to 2000 g of active ingredient per hectare,more preferably 10 to 1000 g/ha, most preferably 10 to 600 g/ha. Whenused as seed drenching agent, convenient dosages are from 10 mg to 1 gof active substance per kg of seeds.

When the combinations of the present invention are used for treatingseed, rates of 0.001 to 50 g of a compound of formula (I) per kg ofseed, preferably from 0.01 to 10 g per kg of seed are generallysufficient.

Suitably, a composition comprising a compound of formula (I) accordingto the present invention is applied either preventative, meaning priorto disease development or curative, meaning after disease development.

The compositions of the invention may be employed in any conventionalform, for example in the form of a twin pack, a powder for dry seedtreatment (DS), an emulsion for seed treatment (ES), a flowableconcentrate for seed treatment (FS), a solution for seed treatment (LS),a water dispersible powder for seed treatment (WS), a capsule suspensionfor seed treatment (CF), a gel for seed treatment (GF), an emulsionconcentrate (EC), a suspension concentrate (SC), a suspo-emulsion (SE),a capsule suspension (CS), a water dispersible granule (WG), anemulsifiable granule (EG), an emulsion, water in oil (EO), an emulsion,oil in water (EW), a micro-emulsion (ME), an oil dispersion (OD), an oilmiscible flowable (OF), an oil miscible liquid (OL), a solubleconcentrate (SL), an ultra-low volume suspension (SU), an ultra-lowvolume liquid (UL), a technical concentrate (TK), a dispersibleconcentrate (DC), a wettable powder (WP) or any technically feasibleformulation in combination with agriculturally acceptable adjuvants.

Such compositions may be produced in conventional manner, e.g. by mixingthe active ingredients with appropriate formulation inerts (diluents,solvents, fillers and optionally other formulating ingredients such assurfactants, biocides, anti-freeze, stickers, thickeners and compoundsthat provide adjuvancy effects). Also conventional slow releaseformulations may be employed where long lasting efficacy is intended.Particularly formulations to be applied in spraying forms, such as waterdispersible concentrates (e.g. EC, SC, DC, OD, SE, EW, EO and the like),wettable powders and granules, may contain surfactants such as wettingand dispersing agents and other compounds that provide adjuvancyeffects, e.g. the ondensation product of formaldehyde with naphthalenesulphonate, an alkylarylsulphonate, a lignin sulphonate, a fatty alkylsulphate, and ethoxylated alkylphenol and an ethoxylated fatty alcohol.

A seed dressing formulation is applied in a manner known per se to theseeds employing the combination of the invention and a diluent insuitable seed dressing formulation form, e.g. as an aqueous suspensionor in a dry powder form having good adherence to the seeds. Such seeddressing formulations are known in the art. Seed dressing formulationsmay contain the single active ingredients or the combination of activeingredients in encapsulated form, e.g. as slow release capsules ormicrocapsules.

In general, the formulations include from 0.01 to 90% by weight ofactive agent, from 0 to 20% agriculturally acceptable surfactant and 10to 99.99% solid or liquid formulation inerts and adjuvant(s), the activeagent consisting of at least the compound of formula (I) together withcomponent (B) and (C), and optionally other active agents, particularlymicrobiocides or conservatives or the like. Concentrated forms ofcompositions generally contain in between about 2 and 80%, preferablybetween about 5 and 70% by weight of active agent. Application forms offormulation may for example contain from 0.01 to 20% by weight,preferably from 0.01 to 5% by weight of active agent. Whereas commercialproducts will preferably be formulated as concentrates, the end userwill normally employ diluted formulations.

Whereas it is preferred to formulate commercial products asconcentrates, the end user will normally use dilute formulations.

EXAMPLES

The Examples which follow serve to illustrate the invention. Certaincompounds of the invention can be distinguished from known compounds byvirtue of greater efficacy at low application rates, which can beverified by the person skilled in the art using the experimentalprocedures outlined in the Examples, using lower application rates ifnecessary, for example 50 ppm, 12.5 ppm, 6 ppm, 3 ppm, 1.5 ppm, 0.8 ppmor 0.2 ppm.

Throughout this description, temperatures are given in degrees Celsiusand “m.p.” means melting point. LC/MS means Liquid Chromatography MassSpectroscopy and the description of the apparatus and the methods are:

Method G:

Spectra were recorded on a Mass Spectrometer from Waters (SQD, SQDIISingle quadrupole mass spectrometer) equipped with an electrospraysource (Polarity: positive and negative ions), Capillary: 3.00 kV, Conerange: 30 V, Extractor: 2.00 V, Source Temperature: 150° C., DesolvationTemperature: 350° C., Cone Gas Flow: 50 l/h, Desolvation Gas Flow: 650l/h, Mass range: 100 to 900 Da) and an Acquity UPLC from Waters: Binarypump, heated column compartment, diode-array detector and ELSD detector.Column: Waters UPLC HSS T3, 1.8 μm, 30×2.1 mm, Temp: 60° C., DADWavelength range (nm): 210 to 500, Solvent Gradient: A=water+5%MeOH+0.05% HCOOH, B=Acetonitrile+0.05% HCOOH, gradient: 10-100% B in 1.2min; Flow (ml/min) 0.85

Method H:

Spectra were recorded on a Mass Spectrometer from Waters (SQD, SQDIISingle quadrupole mass spectrometer) equipped with an electrospraysource (Polarity: positive and negative ions), Capillary: 3.00 kV, Conerange: 30V, Extractor: 2.00 V, Source Temperature: 150° C., DesolvationTemperature: 350° C., Cone Gas Flow: 50 l/h, Desolvation Gas Flow: 650l/h, Mass range: 100 to 900 Da) and an Acquity UPLC from Waters: Binarypump, heated column compartment, diode-array detector and ELSD detector.Column: Waters UPLC HSS T3, 1.8 μm, 30×2.1 mm, Temp: 60° C., DADWavelength range (nm): 210 to 500, Solvent Gradient: A=water+5%MeOH+0.05% HCOOH, B=Acetonitrile+0.05% HCOOH, gradient: 10-100% B in 2.7min; Flow (ml/min) 0.85

Method W:

Spectra were recorded on a Mass Spectrometer (ACQUITY UPLC) from Waters(SQD, SQDII Single quadrupole mass spectrometer) equipped with anelectrospray source (Polarity: positive or negative ions, Capillary: 3.0kV, Cone: 30V, Extractor: 3.00 V, Source Temperature: 150° C.,Desolvation Temperature: 400° C., Cone Gas Flow: 60 L/Hr, DesolvationGas Flow: 700 L/Hr, Mass range: 140 to 800 Da), DAD Wavelength range(nm): 210 to 400, and an Acquity UPLC from Waters: Solvent degasser,binary pump, heated column compartment and diode-array detector. Column:Waters UPLC HSS T3, 1.8 μm, 30×2.1 mm, Temp: 60° C., DAD Wavelengthrange (nm): 210 to 500, Solvent Gradient: A=Water/Methanol 9:1, 0.1%formic acid, B=Acetonitrile+0.1% formic acid, gradient: 0-100% B in 2.5min; Flow (ml/min) 0.75

Method I:

Spectra were recorded on a Mass Spectrometer (ACQUITY UPLC) from Waters(SQD, SQDII or ZQ Single quadrupole mass spectrometer) equipped with anelectrospray source (Polarity: positive or negative ions, Capillary (kV)3.5, Cone (V) 30.00, Extractor (V) 3.00, Source Temperature (° C.) 150,Desolvation Temperature (° C.) 400, Cone Gas Flow (L/Hr) 60, DesolvationGas Flow (L/Hr) 700, Mass range: 140 to 800 Da) and an Acquity UPLC fromWaters: Binary pump, heated column compartment and diode-array detector.Solvent degasser, binary pump, heated column compartment and diode-arraydetector. Solvent degasser, binary pump, heated column compartment anddiode-array detector. Column: Waters ACQUITY UPLC HSS T3; Column length:30 mm; Internal diameter of column: 2.1 mm; Particle Size: 1.8 micron;Temperature: 60° C., DAD Wavelength range (nm): 210 to 400. SolventGradient A: Water/Methanol 9:1, 0.1% formic acid and Solvent B:Acetonitrile, 0.1% formic acid

Time A B Flow rate (minutes) (%) (%) (ml/min) 0 100 0 0.75 2.5 0 1000.75 2.8 0 100 0.75 3.0 100 0 0.75

Formulation Examples

Wettable powders a) b) c) active ingredient [compound of formula (I)]25%  50% 75% sodium lignosulfonate 5%  5% — sodium lauryl sulfate 3% — 5% sodium diisobutylnaphthalenesulfonate —  6% 10% phenol polyethyleneglycol ether —  2% — (7-8 mol of ethylene oxide) highly dispersedsilicic acid 5% 10% 10% Kaolin 62%  27% —The active ingredient is thoroughly mixed with the adjuvants and themixture is thoroughly ground in a suitable mill, affording wettablepowders that can be diluted with water to give suspensions of thedesired concentration.

Powders for dry seed treatment a) b) c) active ingredient [compound offormula (I)] 25% 50% 75% light mineral oil  5%  5%  5% highly dispersedsilicic acid  5%  5% — Kaolin 65% 40% — Talcum — 20%The active ingredient is thoroughly mixed with the adjuvants and themixture is thoroughly ground in a suitable mill, affording powders thatcan be used directly for seed treatment.

Emulsifiable concentrate active ingredient [compound of formula (I)] 10%octylphenol polyethylene glycol ether  3% (4-5 mol of ethylene oxide)calcium dodecylbenzenesulfonate  3% castor oil polyglycol ether (35 molof ethylene oxide)  4% Cyclohexanone 30% xylene mixture 50%Emulsions of any required dilution, which can be used in plantprotection, can be obtained from this concentrate by dilution withwater.

Dusts a) b) c) Active ingredient [compound of formula (I)]  5%  6%  4%talcum 95% — — Kaolin — 94% — mineral filler — — 96%Ready-for-use dusts are obtained by mixing the active ingredient withthe carrier and grinding the mixture in a suitable mill. Such powderscan also be used for dry dressings for seed.

Extruder granules Active ingredient [compound of formula (I)] 15% sodiumlignosulfonate  2% carboxymethylcellulose  1% Kaolin 82%The active ingredient is mixed and ground with the adjuvants, and themixture is moistened with water. The mixture is extruded and then driedin a stream of air.

Coated granules Active ingredient [compound of formula (I)] 8%polyethylene glycol (mol. wt. 200) 3% Kaolin 89% The finely ground active ingredient is uniformly applied, in a mixer, tothe kaolin moistened with polyethylene glycol. Non-dusty coated granulesare obtained in this manner.

Suspension concentrate active ingredient [compound of formula (I)] 40%propylene glycol 10% nonylphenol polyethylene glycol ether (15 mol ofethylene oxide)  6% Sodium lignosulfonate 10% carboxymethylcellulose  1%silicone oil (in the form of a 75% emulsion in water)  1% Water 32%The finely ground active ingredient is intimately mixed with theadjuvants, giving a suspension concentrate from which suspensions of anydesired dilution can be obtained by dilution with water. Using suchdilutions, living plants as well as plant propagation material can betreated and protected against infestation by microorganisms, byspraying, pouring or immersion.

Flowable concentrate for seed treatment active ingredient [compound offormula (I)] 40%  propylene glycol 5% copolymer butanol PO/EO 2%tristyrenephenole with 10-20 moles EO 2% 1,2-benzisothiazolin-3-one (inthe form of a 20% solution 0.5%   in water) monoazo-pigment calcium salt5% Silicone oil (in the form of a 75% emulsion in water) 0.2%   Water45.3%  The finely ground active ingredient is intimately mixed with theadjuvants, giving a suspension concentrate from which suspensions of anydesired dilution can be obtained by dilution with water. Using suchdilutions, living plants as well as plant propagation material can betreated and protected against infestation by microorganisms, byspraying, pouring or immersion.Slow Release Capsule Suspension28 parts of a combination of the compound of formula (I) are mixed with2 parts of an aromatic solvent and 7 parts of toluenediisocyanate/polymethylene-polyphenylisocyanate-mixture (8:1). Thismixture is emulsified in a mixture of 1.2 parts of polyvinylalcohol,0.05 parts of a defoamer and 51.6 parts of water until the desiredparticle size is achieved. To this emulsion a mixture of 2.8 parts1,6-diaminohexane in 5.3 parts of water is added. The mixture isagitated until the polymerization reaction is completed.The obtained capsule suspension is stabilized by adding 0.25 parts of athickener and 3 parts of a dispersing agent. The capsule suspensionformulation contains 28% of the active ingredients. The medium capsulediameter is 8-15 microns.The resulting formulation is applied to seeds as an aqueous suspensionin an apparatus suitable for that purpose.

PREPARATION EXAMPLES Example 1: This Example Illustrates the PreparationofN-[4-cyclopropyl-1-methyl-1-(2,2,2-trifluoroethyl)but-3-ynyl]-8-fluoro-quinoline-3-carboxamideStep 1: Preparation ethyl5-cyclopropyl-2-(2,2,2-trifluoroethyl)pent-4-ynoate

To a solution of ethyl-4,4,4-trifluorobutyrate (1.3 g, 7.49 mmol) intetrahydrofuran (0.33M, 22 mL) was added at −50° C., Lithiumdiisopropylamine (2M) (1.2 eq, 4.5 mL, 8.99 mmol). The solution wasstirred at −50° C. for 1 h. 3-bromoprop-1-ynylcyclopropane (1.2 eq, 1.59g, 8.99 mmol) was added at −50° C. and the brown solution was stirredfrom this temperature to rt for 3h. The reaction mixture was quenchedwith NaHCO₃ saturated aqueous, and extracted twice with ethyl acetate.The organic phase was washed with brine, dried over Na₂SO₄ anhydrous,filtered and concentrated. Purification by flash chromatography to giveethyl 5-cyclopropyl-2-(2,2,2-trifluoroethyl)pent-4-ynoate (0.63 g, 34%yield) as a yellow liquid: LC-MS (Method G), Rt=1.09 min, MS: (M+1)=249;

¹H NMR (400 MHz, CHLOROFORM-d) δ ppm 0.57-0.78 (m, 4H) 1.15-1.22 (m, 1H)1.30 (t, 3H) 2.40-2.83 (m, 5H) 4.21 (q, 2H).

Step 2: Preparation of ethyl5-cyclopropyl-2-methyl-2-(2,2,2-trifluoroethyl)pent-4-ynoate

To a solution of ethyl5-cyclopropyl-2-(2,2,2-trifluoroethyl)pent-4-ynoate (0.63 g, 2.6 mmol)in tetrahydrofuran (0.33M, 8 mL) was added at −50° C., Lithiumdiisopropylamine (2M) (1.3 eq, 1.7 mL, 3.3 mmol). The solution wasstirred at −50° C. for 1 h. Iodomethane (1.2 eq, 0.20 mL, 3.1 mmol) wasadded at −50° C. and the brown solution was stirred from thistemperature to rt for 3 h. The reaction mixture was quenched with NaHCO₃saturated aqueous, and extracted twice with ethyl acetate. The organicphase was washed with brine, dried over Na₂SO₄ anhydrous, filtered andconcentrated. Purification by flash chromatography to give ethyl5-cyclopropyl-2-methyl-2-(2,2,2-trifluoroethyl)pent-4-ynoate (0.42 g,62% yield) as a brown liquid: LC-MS (Method G), Rt=1.12 min, MS:(M+1)=263;

¹H NMR (400 MHz, CHLOROFORM-d) δ ppm 0.58-0.79 (m, 4H) 1.15-1.40 (m, 6H)2.40-2.72 (m, 4H) 4.21 (q, 2H).

¹⁹F (400 MHz, CHLOROFORM-d) δ ppm −61.

Step 3: Preparation of5-cyclopropyl-2-methyl-2-(2,2,2-trifluoroethyl)pent-4-ynoic acid

Ethyl 5-cyclopropyl-2-methyl-2-(2,2,2-trifluoroethyl)pent-4-ynoate (0.42g, 1.07 mmol) was stirred in dioxane (5 mL, 0.3M) and ethanol (5 mL,0.3M). Sodium hydroxide (0.45 g, 7 eq, 11.3 mmol) was added and theyellow solution was stirred at 90° C. for 2h. The reaction mixture wasacidified with HCl (1M) and extracted twice with dichloromethane. Theorganic phase was washed with brine, dried over Na₂SO₄ anhydrous,filtered and concentrated to give5-cyclopropyl-2-methyl-2-(2,2,2-trifluoroethyl)pent-4-ynoic acid (0.29g, 76% yield) as a brown liquid: LC-MS (Method G), Rt=0.95 min, MS:(M+1)=235;

¹H NMR (400 MHz, CHLOROFORM-d) δ ppm ¹H NMR (400 MHz, CHLOROFORM-d) δppm 0.58-0.79 (m, 4H) 1.15-1.25 (m, 1H) 1.40 (s, 3H) 2.45-2.75 (m, 4H).

¹⁹F (400 MHz, CHLOROFORM-d) δ ppm −61.

Step 4: Preparation of (4-methoxyphenyl)methylN-[4-cyclopropyl-1-methyl-1-(2,2,2-trifluoroethyl)but-3-ynyl]carbamate

To a solution of5-cyclopropyl-2-methyl-2-(2,2,2-trifluoroethyl)pent-4-ynoic acid (0.18g, 0.79 mmol) in toluene (4 mL, 0.2M) was added triethylamine (3 eq,0.33 mL, 2.38 mmmol) and diphenylphosphoryl azide (1.6 eq, 0.36 g, 1.27mmol). The brown solution was stirred at rt for 1 h (azide formed).4-methoxybenzyl alcohol (3 eq, 0.30 mL, 2.38 mmol) was then added. Thesolution was stirred 1h at 80° C. then 16h at 110° C. The reactionmixture was slowly quenched into NaHCO₃ saturated aqueous and extractedtwice with ethyl acetate. The organic phase was washed once with athiosulfate solution and once with brine, dried over Na₂SO₄ anhydrous,filtered and concentrated. Purification by flash chromatography to give(4-methoxyphenyl)methylN-[4-cyclopropyl-1-methyl-1-(2,2,2-trifluoroethyl)but-3-ynyl]carbamate(0.21 g, 71% yield) as a colourless liquid LC-MS (Method G), Rt=1.15min, MS: (M+1)=370;

¹H NMR (400 MHz, CHLOROFORM-d) δ ppm 0.60-0.65 (m, 2H) 0.75-0.80 (m, 2H)1.17-1.25 (m, 1H) 1.48 (s, 3H) 2.50-2.65 (m, 3H) 2.95 (m, 1H) 3.82 (s,3H) 4.89 (br, 1H, NH) 5.03 (s, 2H) 6.90 (d, 2H) 7.30 (d, 2H).

¹⁹F (400 MHz, CHLOROFORM-d) δ ppm −60.

Step 5: Preparation of6-cyclopropyl-1,1,1-trifluoro-3-methyl-hex-5-yn-3-amine; hydrochloride

To a solution of 4-methoxyphenyl)methylN-[4-cyclopropyl-1-methyl-1-(2,2,2-trifluoroethyl)but-3-ynyl]carbamate(0.11 g, 0.30 mmol) in dichloromethane (1.5 mL, 0.2M) was added Hydrogenchloride (4M in dioxane) (0.6 mL, 8 eq, 2.38 mmol). The solution wasstirred at rt for 1h. Crude was concentrated to give6-cyclopropyl-1,1,1-trifluoro-3-methyl-hex-5-yn-3-amine; hydrochloride(0.055 g, 76% yield) as a yellow gum, LC-MS (Method G), Rt=0.56 min, MS:(M+1)=206;

¹H NMR (400 MHz, CHLOROFORM-d) δ ppm 0.78 (d, 2H) 1.32 (m, 1H) 1.66 (s,3H) 2.75-2.87 (m, 4H) 8.80 (b, 2H, NH2).

¹⁹F (400 MHz, CHLOROFORM-d) δ ppm −60.

Step 6: Preparation ofN-[4-cyclopropyl-1-methyl-1-(2,2,2-trifluoroethyl)but-3-ynyl]-8-fluoro-quinoline-3-carboxamide

To a solution of6-cyclopropyl-1,1,1-trifluoro-3-methyl-hex-5-yn-3-amine; hydrochloride(0.050 g, 0.21 mmol) in dichloromethane (2.1 mL, 0.1M) and triethylamine(0.12 mL, 4 eq, 0.83 mmol) was addedN-(3-dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride (0.065 g,1.6 eq, 0.33 mmol) followed byO-(7-azabenzotriazole-1-yl)-N,N,N′,N′-tetramethyluroniumhexafluorophosphate (0.13 g, 1.6 eq, 0.33 mmol) and8-fluoroquinoline-3-carboxylic acid (0.079 g. 2 eq, 0.41 mmol). Thesolution was stirred at rt for 16h. The reaction mixture was quenchedwith NaHCO₃ saturated aqueous and extracted twice with dichloromethane.The organic phase was washed with brine, dried over Na₂SO₄ anhydrous,filtered and concentrated. Purification by flash chromatography to giveN-[4-cyclopropyl-1-methyl-1-(2,2,2-trifluoroethyl)but-3-ynyl]-8-fluoro-quinoline-3-carboxamide(0.073 g, 93% yield) as a white solid, mp=110-112° C., LC-MS (Method G),Rt=1.06 min, MS: (M+1)=379;

¹H NMR (400 MHz, CHLOROFORM-d) δ ppm 0.58-0.63 (m, 2H) 0.72-0.78 (m, 2H)1.22 (m, 1H) 1.68 (s, 3H) 2.70-2.82 (m, 2H) 2.92 (d, 1H) 6.47 (s, 1H,NH) 7.51 (m, 1H) 7.58 (m, 1H) 7.70 (d, 1H) 8.55 (s, 1H) 9.22 (s, 1H).

¹⁹F (400 MHz, CHLOROFORM-d) δ ppm −60, −124.5.

Example 2: Preparation of8-fluoro-N-(1-isopropyl-1-methyl-3-phenyl-prop-2-ynyl)quinoline-3-carboxamideStep 1: Preparation of 3,4-dimethyl-1-phenyl-pent-1-yn-3-amine

To a solution of iodobenzene (12.0 mmol, 2.50 g) in a mixture oftetrahydrofuran (61 mL, 0.2 M) and diisopropylamine (30 mL) was added3,4-dimethylpent-1-yn-3-amine hydrochloride (1.20 equiv., 15.0 mmol,2.10 g), copper (I) iodide (0.10 equiv., 1.2 mmol, 0.23 g) andBis(triphenylphosphine)palladium(II) dichloride (0.10 equiv., 1.2 mmol,0.85 g) and the reaction mixture was stirred at room temperature for 20h. The mixture was filtered over a pad of silica gel and the pad waswashed with ethyl acetate. The filtrate was washed with water and brine,dried over anhydrous sodium sulfate, filtered and concentrated. Theresidue was purified by Flash Chromatography to give3,4-dimethyl-1-phenyl-pent-1-yn-3-amine (2.05 g, 10.9 mmol, 90% yield)as a dark yellow oil. Rt=0.86 min (Method H), MS: (M+1)=189;

¹H NMR (400 MHz, CHLOROFORM-d) δ ppm 1.12 (br d, J=2.57 Hz, 6H)1.40-1.55 (m, 3H) 1.77-2.03 (m, 1H) 7.27-7.37 (m, 3H) 7.43 (dd, J=7.52,2.02 Hz, 2H).

Step 2: Preparation of8-fluoro-N-(1-isopropyl-1-methyl-3-phenyl-prop-2-ynyl)quinoline-3-carboxamide

To a suspension of 8-fluoroquinoline-3-carboxylic acid (1.0 mmol, 0.20g) in dichloromethane (5.2 mL, 0.2 M) was added triethylamine (1.5equiv., 1.6 mmol, 0.22 mL) followed byN-(3-dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride (1.5equiv., 1.6 mmol, 0.31 g), 1-hydroxy-7-azabenzotriazole (1.5 equiv., 1.6mmol, 0.22 g) and 3,4-dimethyl-1-phenyl-pent-1-yn-3-amine (1.0 equiv.,1.0 mmol, 0.20 g) and the mixture was stirred at room temperature for 2h 30 min. The reaction mixture was diluted with ethyl acetate. Themixture was washed with an aqueous solution of citric acid (1 M),saturated aqueous bicarbonate solution, brine, dried over anhydroussodium sulfate, filtered and concentrated to afford8-fluoro-N-(1-isopropyl-1-methyl-3-phenyl-prop-2-ynyl)quinoline-3-carboxamide(0.26 g, 0.72 mmol, 69% yield) as a brown solid. Rt=1.83 min (Method H),MS: (M+1)=361.6;

¹H NMR (400 MHz, CHLOROFORM-d) δ ppm 1.19 (dd, J=8.99, 6.79 Hz, 6H) 1.96(s, 3H) 2.77-2.95 (m, 1H) 6.47-6.58 (m, 1H) 7.32-7.41 (m, 3H) 7.49-7.56(m, 3H) 7.56-7.63 (m, 1H) 7.70-7.82 (m, 1H) 8.55-8.68 (m, 1H) 9.25-9.41(m, 1H); ¹⁹F NMR (377 MHz, CHLOROFORM-d) δ ppm −129.84-−118.63 (m, 1F).

Example 3: Preparation of the Single Isomers of8-fluoro-N-(1-isopropyl-1-methyl-3-phenyl-prop-2-ynyl)quinoline-3-carboxamide

The racemic8-fluoro-N-(1-isopropyl-1-methyl-3-phenyl-prop-2-ynyl)quinoline-3-carboxamidemixture was submitted to chiral resolution by preparative HPLCchromatography using the conditions outlined hereafter to deliver(S)-8-fluoro-N-(1-isopropyl-1-methyl-3-phenyl-prop-2-ynyl)quinoline-3-carboxamideand(R)-8-fluoro-N-(1-isopropyl-1-methyl-3-phenyl-prop-2-ynyl)quinoline-3-carboxamide.

Analytical HPLC Method:

SFC:

Waters Acquity UPC²/QDa

PDA Detector Waters Acquity UPC²

Column: Daicel SFC CHIRALPAK® IF, 3 □m, 0.3 cm×10 cm, 40° C.

Mobile phase: A: CO₂ B: MeOH gradient: 20-40% B in 1.8 min

ABPR: 1800 psi

Flow rate: 2.0 ml/min

Detection: 240 nm

Sample concentration: 1 mg/mL in Hept/iPr 50/50

Injection: 1 μL

Preparative HPLC Method:

Autopurification System from Waters: 2767 sample Manager, 2489 UVNisibleDetector,

2545 Quaternary Gradient Module.

Column: Daicel CHIRALPAK® IF, 5 μm, 1.0 cm×25 cm

Mobile phase: Hept/EtOH 95/05

Flow rate: 10 ml/min

Detection: UV 240 nm

Sample concentration: 60 mg/mL in/EtOAc

Injection: 80-160 μl

First eluting enantiomer Second eluting enantiomer Retention time (min)~1.23 Retention time (min) ~1.52 Chemical purity (area % Chemical purity(area % at 240 nm) 99 at 240 nm) 99 Enantiomeric excess (%) >99Enantiomeric excess (%) >99

Example 4: Preparation ofN-(8-fluoro-2-methyl-3-quinolyl)-2,2-dimethyl-4-(o-tolyl)but-3-ynamideStep 1: Preparation ofN-(8-fluoro-2-methyl-3-quinolyl)-2,2-dimethyl-but-3-ynamide

To a solution of 2,2-dimethylbut-3-ynoic acid (8.9 mmol, 1.0 g) indichloroethane (45 mL, 0.2 M) was added triethylamine (1.5 equiv., 13mmol, 1.9 mL) followed by N-(3-dimethylaminopropyl)-N′-ethylcarbodiimidehydrochloride (1.5 equiv., 13 mmol, 2.6 g), 1-hydroxy-7-azabenzotriazole(1.5 equiv., 13 mmol, 1.9 g) and 8-fluoro-2-methyl-quinolin-3-amine (1.0equiv., 8.9 mmol, 1.6 g) and the mixture was stirred at 60° C. for 20 h.The reaction mixture was cooled down to room temperature and dilutedwith ethyl acetate. The mixture was then washed with an aqueous solutionof citric acid (1 M), saturated aqueous bicarbonate solution, brine,dried over anhydrous sodium sulfate, filtered and concentrated. Theresidue was purified by flash chromatography to affordN-(8-fluoro-2-methyl-3-quinolyl)-2,2-dimethyl-but-3-ynamide (1.7 g, 6.3mmol, 71% yield) as a brown solid. Mp 132-135° C., Rt=1.33 min (MethodH), MS: (M+1)=271.4;

¹H NMR (400 MHz, CHLOROFORM-d) δ ppm 1.66 (s, 6H) 2.74-2.80 (m, 1H)2.80-2.85 (m, 3H) 7.30-7.36 (m, 1H) 7.44 (td, J=7.98, 4.95 Hz, 2H) 7.59(d, J=8.07 Hz, 1H) 8.94 (br s, 1H) 9.04 (d, J=1.47 Hz, 1H); ¹⁹F NMR (377MHz, CHLOROFORM-d) δ ppm −126.81 (s, 1F)

Step 2: Preparation ofN-(8-fluoro-2-methyl-3-quinolyl)-2,2-dimethyl-4-(o-tolyl)but-3-ynamide

To a solution of 1-iodo-2-methylbenzene (0.92 mmol, 0.21 g) in a mixtureof tetrahydrofuran (4.6 mL, 0.2 M) and diisopropylamine (2.3 mL) wasadded N-(8-fluoro-2-methyl-3-quinolyl)-2,2-dimethyl-but-3-ynamide (1.0equiv., 0.92 mmol, 0.25 g), copper (I) iodide (0.10 equiv., 0.092 mmol,0.018 g) and Bis(triphenylphosphine)palladium(II) dichloride (0.10equiv., 1.2 mmol, 0.017 g) and the reaction mixture was stirred at roomtemperature for 20 h. The mixture was filtered over a pad of silica geland the pad was washed with ethyl acetate. The filtrate was washed withwater and brine, dried over anhydrous sodium sulfate, filtered andconcentrated. The residue was purified by Flash Chromatography to giveN-(8-fluoro-2-methyl-3-quinolyl)-2,2-dimethyl-4-(o-tolyl)but-3-ynamide(0.22 g, 0.61 mmol, 66% yield) as a dark brown resin. Rt=1.98 min(Method H), MS: (M+1)=361.5;

¹H NMR (400 MHz, CHLOROFORM-d) δ ppm 1.54-1.97 (m, 1H) 1.70-1.82 (m, 1H)1.76 (s, 4H) 2.52 (s, 3H) 2.77 (s, 3H) 7.20-7.27 (m, 1H) 7.27-7.37 (m,3H) 7.40-7.48 (m, 1H) 7.48-7.52 (m, 1H) 7.57-7.63 (m, 1H) 9.01 (s, 1H)9.05-9.13 (m, 1H);

¹⁹F NMR (377 MHz, CHLOROFORM-d) δ ppm −126.60 (br s, 1F)

TABLE E Physical data of compounds of formula I wherein A is C(R₈)(R₉);[M + H] RT (meas- MP Entry IUPAC name STRUCTURE (min) ured) Method ° C.E-1 N-[4-cyclopropyl-1- methyl-1-(2,2,2- trifluoroethyl)but-3-ynyl]-8-fluoro- quinoline-3- carboxamide

1.05 379 G   110- 112 E-2 8-fluoro-N-(1- isobutyl-1-methyl- but-3-ynyl)quinoline-3- carboxamide

1.01 313 G

TABLE F Physical data of compounds of formula I wherein A is a directbond: [M + H] RT (meas- MP Entry IUPAC name STRUCTURE (min) ured) Method° C. F-1 N-(1-isopropyl-3- phenyl-prop-2-ynyl)- 8-methyl-quinoline-3-carboxamide

1.15 344 G F-2 8-chloro-N-(1- isopropyl-3-phenyl- prop-2-ynyl)quinoline-3- carboxamide

1.13 363 G   168- 170 F-3 8-fluoro-N-(1- isopropyl-3-phenyl- prop-2-ynyl)quinoline-3- carboxamide

1.07 347 G   156- 158 F-4 8-fluoro-N-[4,4,4- trifluoro-1-(2-phenylethynyl)butyl] quinoline-3- carboxamide

1.78 401 H F-5 N-(1-tert-butyl-3- phenyl-prop-2-ynyl)-8-fluoro-quinoline-3- carboxamide

1.12 361 G   179- 181 F-6 N-(1,1-diethyl-3- phenyl-prop-2-ynyl)-8-fluoro-quinoline-3- carboxamide

1.81 361 I F-7 N-[1,3-dimethyl-1-(2- phenylethynyl)butyl]-8-fluoro-quinoline-3- carboxamide

1.98 375 H   138- 141 F-9 N-(1-ethyl-1-methyl- 3-phenyl-prop-2-ynyl)-8-methyl- quinoline-3- carboxamide

1.93 343 H   135- 137 F- 10 8-cyano-N-(1-ethyl-1- methyl-3-phenyl-prop-2- ynyl)quinoline-3- carboxamide

1.74 354 H   172- 174 F- 11 8-chloro-N-(1-ethyl- 1-methyl-3-phenyl-prop-2- ynyl)quinoline-3- carboxamide

1.83 363 H   161- 162 F- 12 8-fluoro-N-[3-(2- fluorophenyl)-1-isopropyl-1-methyl- prop-2- ynyl]quinoline-3- carboxamide

1.79 379 H F- 13 8-fluoro-N-[1- isopropyl-1-methyl-3- (o-tolyl)prop-2-ynyl]quinoline-3- carboxamide

1.91 375 H   138- 141 F- 14 N-[1-ethyl-1-methyl- 3-(o-tolyl)prop-2-ynyl]-8-fluoro-2- methyl-quinoline-3- carboxamide

1.84 376 H F- 15 N-[1-ethyl-1-methyl- 3-(o-tolyl)prop-2- ynyl]-8-fluoro-quinoline-3- carboxamide

1.82 362 H   143- 146 F- 16 N-(1-ethyl-1-methyl- 3-phenyl-prop-2-ynyl)-8-fluoro-2- methyl-quinoline-3- carboxamide

1.72 362 H F- 17 N-(1-ethyl-1-methyl- 3-phenyl-prop-2- ynyl)-8-fluoro-quinoline-3- carboxamide

1.69 348 H   129- 132 F- 18 8-fluoro-N-[3-(2- fluorophenyl)-1,1-dimethyl-prop-2- ynyl]quinoline-3- carboxamide

1.55 351 I F- 19 N-[3-(5-cyano-2- methyl-phenyl)-1,1- dimethyl-prop-2-ynyl]-8-fluoro- quinoline-3- carboxamide

1.57 372 I F- 20 N-[3-(3,4- difluorophenyl)-1,1- dimethyl-prop-2-ynyl]-8-fluoro- quinoline-3- carboxamide

1.63 369 I F- 21 N-[1,1-dimethyl-3-(p- tolyl)prop-2-ynyl]-8-fluoro-quinoline-3- carboxamide

1.67 347 I F- 22 N-[3-(2,5- dimethylphenyl)-1,1- dimethyl-prop-2-ynyl]-8-fluoro- quinoline-3- carboxamide

1.79 361 I F- 23 N-[3-(5-chloro-2- methoxy-phenyl)-1,1- dimethyl-prop-2-ynyl]-8-fluoro- quinoline-3- carboxamide

1.67 397 I F- 24 8-fluoro-N-[3-(5- fluoro-2-methyl-phenyl)-1,1-dimethyl- prop-2- ynyl]quinoline-3- carboxamide

1.7 365 I F- 25 N-[3-(2,4- difluorophenyl)-1,1- dimethyl-prop-2-ynyl]-8-fluoro- quinoline-3- carboxamide

1.6 369 I F- 26 N-[3-(2,3- dimethylphenyl)-1,1- dimethyl-prop-2-ynyl]-8-fluoro- quinoline-3- carboxamide

1.76 361 I F- 27 8-fluoro-N-[3-(4- fluorophenyl)-1,1- dimethyl-prop-2-ynyl]quinoline-3- carboxamide

1.58 351 I F- 28 8-fluoro-N-[3-(4- methoxyphenyl)-1,1- dimethyl-prop-2-ynyl]quinoline-3- carboxamide

1.54 363 I F- 29 8-fluoro-N-[3-(3- methoxyphenyl)-1,1- dimethyl-prop-2-ynyl]quinoline-3- carboxamide

1.56 363 I F- 30 N-[3-(3,5- dimethylphenyl)-1,1- dimethyl-prop-2-ynyl]-8-fluoro- quinoline-3- carboxamide

1.79 361 I F- 31 N-[3-(2-cyano-5- methyl-phenyl)-1,1- dimethyl-prop-2-ynyl]-8-fluoro- quinoline-3- carboxamide

1.79 372 I F- 32 N-[3-(3,4- dimethylphenyl)-1,1- dimethyl-prop-2-ynyl]-8-fluoro- quinoline-3- carboxamide

1.76 361 I F- 33 N-[3-(2,4- dimethylphenyl)-1,1- dimethyl-prop-2-ynyl]-8-fluoro- quinoline-3- carboxamide

1.78 361 I F- 34 N-[3-(4-cyano-2- methyl-phenyl)-1,1- dimethyl-prop-2-ynyl]-8-fluoro- quinoline-3- carboxamide

1.57 372 I F- 35 N-[1,1-dimethyl-3-(5- methyl-2- thienyl)prop-2-ynyl]-8-fluoro-quinoline-3- carboxamide

1.62 353 I F- 36 N-[3-(3- cyanophenyl)-1,1- dimethyl-prop-2-ynyl]-8-fluoro- quinoline-3- carboxamide

1.46 358 I F- 37 8-fluoro-N-[3-(2- methoxyphenyl)-1,1- dimethyl-prop-2-ynyl]quinoline-3- carboxamide

1.51 363 I F- 38 N-[3-(4-chloro-3- methoxy-phenyl)-1,1- dimethyl-prop-2-ynyl]-8-fluoro- quinoline-3- carboxamide

1.68 397 I F- 39 N-[1,1-dimethyl-3-(m- tolyl)prop-2-ynyl]-8-fluoro-quinoline-3- carboxamide

1.67 347 I F- 40 N-[3-(3,5- difluorophenyl)-1,1- dimethyl-prop-2-ynyl]-8-fluoro- quinoline-3- carboxamide

1.65 369 I F- 41 N-[3-(2- cyanophenyl)-1,1- dimethyl-prop-2-ynyl]-8-fluoro- quinoline-3- carboxamide

1.43 358 I F- 42 N-[1,1-dimethyl-3-[4- (trifluoromethyl)phenyl]prop-2-ynyl]-8- fluoro-quinoline-3- carboxamide

1.76 401 I F- 43 8-fluoro-N-[3-[2- methoxy-5- (trifluoromethyl)phenyl]-1,1-dimethyl-prop- 2-ynyl]quinoline-3- carboxamide

1.72 431 I F- 44 8-fluoro-N-[3-(3- fluoro-4-methoxy-phenyl)-1,1-dimethyl- prop-2- ynyl]quinoline-3- carboxamide

1.56 381 I F- 45 8-fluoro-N-[3-(2- fluoro-5-methyl-phenyl)-1,1-dimethyl- prop-2- ynyl]quinoline-3- carboxamide

1.67 365 I F- 46 8-fluoro-N-(1- isopropyl-1-methyl-3- phenyl-prop-2-ynyl)quinoline-3- carboxamide

1.83 362 H   118- 122 F- 47 N-[1,1-dimethyl-3-(o- tolyl)prop-2-ynyl]-8-fluoro-quinoline-3- carboxamide

1.72 348 H   156- 160 F- 48 N-[1,1-dimethyl-3-[3-(trifluoromethyl)phenyl] prop-2-ynyl]-8- fluoro-quinoline-3- carboxamide

1.85 402 H   181- 184 F- 49 N-(1,1-dimethyl-3- phenyl-prop-2-ynyl)quinoline-3- carboxamide

1.55 316 H   136- 141 F- 50 N-(1,1-dimethyl-3- phenyl-prop-2-ynyl)-8-fluoro-2-methyl- quinoline-3- carboxamide

1.62 348 H   118- 123 F- 51 N-(1,1-dimethyl-3- phenyl-prop-2-ynyl)-8-fluoro-4-methyl- quinoline-3- carboxamide

1.59 348 H F- 52 8-fluoro-N-(4- methoxy-1,1- dimethyl-but-2-ynyl)quinoline-3- carboxamide

0.82 301 G F- 53 N-(1,1-dimethylbut-2- ynyl)-8-fluoro- quinoline-3-carboxamide

0.85 271 G F- 54 N-(1,1-dimethylprop- 2-ynyl)-8-fluoro- quinoline-3-carboxamide

0.78 257 G   148- 150 F- 55 N-(1,1-dimethyl-3- phenyl-prop-2-ynyl)-8-fluoro-quinoline-3- carboxamide

1.54 333 H   151- 155

TABLE G Physical data of compounds of formula I as individualenantiomers: [M + H] RT (meas- MP Entry IUPAC name STRUCTURE (min) ured)Method (chiral) ° C. G- 1 N-[(1R)-4- cyclopropyl-1- methyl-1-(2,2,2-trifluoroethyl)but- 3-ynyl]-8-fluoro- quinoline-3- carboxamide

2.73 379 SFC: Waters Acquity UPC²/QDa PDA Detector Waters Acquity UPC²G- 2 N-[(1S)-4- cyclopropyl-1- methyl-1-(2,2,2- trifluoroethyl)but-3-ynyl]-8-fluoro- quinoline-3- carboxamide

1.39 379 Column: Daicel SFC CHIRALPAK ® IF, 3 μm, 0.3 cm × 10 cm, 40° C.Mobile phase: A: CO₂ B: MeOH gradient: 20- 40% B in 1.8 min ABPR: 1800psi Flow rate: 2.0 ml/min Detection: 240 nm Sample concentration: 1mg/mL in Hept/iPr 50/50 Injection: 1 μL G- 3 8-fluoro-N-[(1R)-3-methyl-1-(2- phenylethynyl) butyl]quinoline-3- carboxamide

1.45 361 SFC: Waters Acquity UPC²/QDa PDA Detector Waters Acquity UPC²G- 4 8-fluoro-N-[(1S)- 3-methyl-1-(2- phenylethynyl) butyl]quinoline-3-carboxamide

1.05 361 Column: Daicel SFC CHIRALPAK ® IA, 3 μm, 0.3 cm × 10 cm, 40° C.Mobile phase: A: CO2 B: MeOH gradient: 25% B in 1.8 min ABPR: 1800 psiFlow rate: 2.0 ml/min Detection: 237 nm Sample concentration: 1 mg/mL inHept/iPr 50/50 Injection: 1 μL G- 5 N-[(1S)-1,3- dimethyl-1-(2-phenylethynyl) butyl]-8-fluoro- quinoline-3- carboxamide

1.29 375 SFC: Waters Acquity UPC²/QDa PDA Detector Waters Acquity UPC²  124- 127 G- 6 N-[(1R)-1,3- dimethyl-1-(2- phenylethynyl)butyl]-8-fluoro- quinoline-3- carboxamide

1.11 375 Column: Daicel SFC CHIRALPAK ® IF, 3 μm, 0.3 cm × 10 cm, 40° C.Mobile phase: A: CO2 B: MeOH gradient: 20- 40% B in 1.8 min ABPR: 1800psi Flow rate: 2.0 ml/min Detection: 240   128- 130 nm Sampleconcentration: 1 mg/mL in Hept/iPr 50/50 Injection: 1 μL G- 78-fluoro-N-[(1S)- 1-isopropyl-1- methyl-3- phenyl-prop-2-ynyl]quinoline-3- carboxamide

1.52 361 SFC: Waters Acquity UPC²/QDa PDA Detector Waters Acquity UPC²G- 8 8-fluoro-N-[(1R)- 1-isopropyl-1- methyl-3- phenyl-prop-2-ynyl]quinoline-3- carboxamide

1.23 361 Column: Deicel SFC CHIRALPAK ® IF, 3 μm, 0.3 cm × 10 cm, 40° C.Mobile phase: A: CO2 B: MeOH gradient: 20- 40% B in 1.8 min ABPR: 1800psi Flow rate: 2.0 ml/min Detection: 240 nm Sample concentration: 1mg/mL in Hept/iPr 50/50 Injection: 1 μL

Biological Examples

Botryotinia fuckeliana (Botrytis cinerea)/Liquid Culture (Gray Mould)

Conidia of the fungus from cryogenic storage are directly mixed intonutrient broth (Vogels broth). After placing a (DMSO) solution of testcompound into a microtiter plate (96-well format), the nutrient brothcontaining the fungal spores is added. The test plates are incubated at24° C. and the inhibition of growth is determined photometrically 3-4days after application.

The following compounds of Table E gave at least 80% disease control at200 ppm when compared to untreated control leaf disks under the sameconditions, which show extensive disease development:

E-1, E-2, F-1, F-3, F-4, F-5, F-6, F-7, F-9, F-10, F-11, F-12, F-13,F-14, F-15, F-16, F-17, F-18, F-19, F-20, F-21, F-22, F-23, F-24, F-25,F-26, F-27, F-28, F-29, F-30, F-32, F-33, F-34, F-35, F-36, F-37, F-38,F-39, F-40, F-41, F-42, F-43, F-45, F-46, F-47, F-48, F-49, F-50, F-51,F-55, G-1, G-2, G-3, G-4, G-5, G-6, G-7, G-8Fusarium culmorum/Liquid Culture (Head Blight)Conidia of the fungus from cryogenic storage are directly mixed intonutrient broth (PDB potato dextrose broth). After placing a (DMSO)solution of test compound into a microtiter plate (96-well format), thenutrient broth containing the fungal spores is added. The test platesare incubated at 24° C. and the inhibition of growth is determinedphotometrically 3-4 days after application.

The following compounds of Table E gave at least 80% disease control at200 ppm when compared to untreated control leaf disks under the sameconditions, which show extensive disease development:

E-1, E-2, F-1, F-2, F-3, F-4, F-5, F-6, F-7, F-9, F-10, F-11, F-12,F-13, F-14, F-15, F-16, F-17, F-18, F-19, F-20, F-21, F-22, F-23, F-24,F-25, F-26, F-27, F-28, F-29, F-30, F-32, F-33, F-34, F-35, F-36, F-37,F-38, F-39, F-40, F-41, F-42, F-43, F-45, F-46, F-47, F-48, F-49, F-50,F-51, F-53, F-54, F-55, G-1, G-2, G-3, G-4, G-5, G-6, G-7, G-8Glomerella lagenarium (Colletotrichum lagenarium)/Liquid Culture(Anthracnose)

Conidia of the fungus from cryogenic storage are directly mixed intonutrient broth (PDB potato dextrose broth). After placing a (DMSO)solution of test compound into a microtiter plate (96-well format), thenutrient broth containing the fungal spores is added. The test platesare incubated at 24° C. and the inhibition of growth is measuredphotometrically 3-4 days after application.

The following compounds of Table E gave at least 80% disease control at200 ppm when compared to untreated control leaf disks under the sameconditions, which show extensive disease development:

E-1, E-2, F-3, F-5, F-6, F-7, F-9, F-10, F-11, F-12, F-13, F-14, F-15,F-16, F-17, F-18, F-19, F-20, F-21, F-22, F-23, F-24, F-25, F-26, F-27,F-28, F-29, F-30, F-32, F-33, F-37, F-38, F-39, F-40, F-41, F-42, F-43,F-45, F-46, F-47, F-48, F-49, F-50, F-51, F-53, F-55, G-3, G-4, G-5,G-7, G-8Monographella nivalis (Microdochium nivale)/Liquid Culture (Foot RotCereals)

Conidia of the fungus from cryogenic storage are directly mixed intonutrient broth (PDB potato dextrose broth). After placing a (DMSO)solution of test compound into a microtiter plate (96-well format), thenutrient broth containing the fungal spores is added. The test platesare incubated at 24° C. and the inhibition of growth is determinedphotometrically 4-5 days after application.

The following compounds of Table E gave at least 80% disease control at200 ppm when compared to untreated control leaf disks under the sameconditions, which show extensive disease development:

E-1, F-1, F-2, F-3, F-4, F-5, F-6, F-7, F-9, F-10, F-11, F-12, F-13,F-15, F-16, F-17, F-18, F-19, F-20, F-21, F-23, F-24, F-25, F-26, F-27,F-28, F-29, F-30, F-32, F-33, F-34, F-35, F-36, F-37, F-38, F-39, F-40,F-41, F-42, F-45, F-46, F-47, F-48, F-49, F-51, F-54, F-55, G-1, G-3,G-5, G-6, G-7, G-8Mycosphaerella graminicola (Septoria tritici)/Liquid Culture (SeptoriaBlotch)

Conidia of the fungus from cryogenic storage are directly mixed intonutrient broth (PDB potato dextrose broth). After placing a (DMSO)solution of test compound into a microtiter plate (96-well format), thenutrient broth containing the fungal spores is added. The test platesare incubated at 24° C. and the inhibition of growth is determinedphotometrically 4-5 days after application.

The following compounds of Table E gave at least 80% disease control at200 ppm when compared to untreated control leaf disks under the sameconditions, which show extensive disease development:

E-1, F-3, F-4, F-5, F-7, G-3

Magnaporthe grisea (Pyricularia oryzae)/Liquid Culture (Rice Blast)

Conidia of the fungus from cryogenic storage are directly mixed intonutrient broth (PDB potato dextrose broth). After placing a (DMSO)solution of test compound into a microtiter plate (96-well format), thenutrient broth containing the fungal spores is added. The test platesare incubated at 24° C. and the inhibition of growth is determinedphotometrically 3-4 days after application.

The following compounds gave at least 80% control of Magnaporthe griseaat 20 ppm when compared to untreated control under the same conditions,which showed extensive disease development:

F-1, F-3, F-4, F-5, F-7, F-9, F-10, F-11, F-12, F-13, F-14, F-15, F-16,F-17, F-46, F-47, F-48, F-49, F-50, F-51, G-3, G-4, G-5, G-6, G-7, G-8

Fusarium culmorum/Wheat/Spikelet Preventative (Head Blight)

Wheat spikelets cv. Monsun are placed on agar in multiwell plates(24-well format) and sprayed with the formulated test compound dilutedin water. The spikelets are inoculated with a spore suspension of thefungus 1 day after application. The inoculated spikelets are incubatedat 20° C. and 60% rh under a light regime of 72 h semi darkness followedby 12 h light/12 h darkness in a climate chamber and the activity of acompound is assessed as percent disease control compared to untreatedwhen an appropriate level of disease damage appears on untreated checkspikelets (6-8 days after application).

The following compounds gave at least 80% control of Fusarium culmorumat 200 ppm when compared to untreated control under the same conditions,which showed extensive disease development:

F-3, F-7, F-9, F-10, F-11, F-12, F-14, F-16, F-17, F-24, F-25, F-28,F-29, F-39, F-40, F-45, F- 46, F-47, F-49, G-4, G-7

Pyrenophora teres/Barley/Leaf Disc Preventative (Net Blotch)

Barley leaf segments cv. Hasso are placed on agar in a multiwell plate(24-well format) and sprayed with the formulated test compound dilutedin water. The leaf segmens are inoculated with a spore suspension of thefungus 2 days after application. The inoculated leaf segments areincubated at 20° C. and 65% rh under a light regime of 12 h light/12 hdarkness in a climate cabinet and the activity of a compound is assessedas disease control compared to untreated when an appropriate level ofdisease damage appears in untreated check leaf segments (5-7 days afterapplication).

The following compounds gave at least 80% control of Pyrenophora teresat 200 ppm when compared to untreated control under the same conditions,which showed extensive disease development:

F-1, F-2, F-11, F-17, F-21, F-29, F-35, F-55, G-4

Sclerotinia sclerotiorum/Liquid Culture (Cottony Rot)

Mycelia fragments of a newly grown liquid culture of the fungus aredirectly mixed into nutrient broth (Vogels broth). After placing a(DMSO) solution of test compound into a microtiter plate (96-wellformat) the nutrient broth containing the fungal material is added. Thetest plates are incubated at 24° C. and the inhibition of growth isdetermined photometrically 3-4 days after application.

The following compounds gave at least 80% control of Sclerotiniasclerotiorum at 20 ppm when compared to untreated control under the sameconditions, which showed extensive disease development:

F-5, F-7, F-9, F-10, F-11, F-12, F-15, F-50, F-51, G-5, G-7

Gaeumannomyces graminis/Liquid Culture (Take-All of Cereals)

Mycelial fragments of the fungus from cryogenic storage were directlymixed into nutrient broth (PDB potato dextrose broth). After placing a(DMSO) solution of test compound into a microtiter plate (96-wellformat), the nutrient broth containing the fungal spores is added. Thetest plates are incubated at 24° C. and the inhibition of growth isdetermined photometrically 4-5 days after application. The followingcompounds gave at least 80% control of Gaeumannomyces graminis at 20 ppmwhen compared to untreated control under the same conditions, whichshowed extensive disease development:

F-4, F-5, F-6, F-7, F-10, F-12, F-13, F-23, F-24, F-25, F-46, F-47,F-48, F-49, F-51, F-55, G-3, G-4, G-5, G-6, G-8

What is claimed is:
 1. A compound of formula ( )

wherein X is O or S; R₁ is hydrogen, halogen, methyl, or cyano; R₂ ishydrogen, methyl or halogen; R₃ and R₄ are each independently selectedfrom hydrogen, halogen or methyl; R₅ is C₁-C₆ alkyl, C₂-C₆ alkenyl,C₃-C₇ cycloalkyl or C₃-C₄ cycloalkyl(C₁-C₃)alkyl, wherein the alkyl,alkenyl and cycloalkyl groups may be optionally substituted with 1 to 3substituents independently selected from halogen, cyano, C₁-C₃ alkyl,C₁-C₃ alkoxy and C₁-C₃ alkylthio; R₆ is hydrogen, cyano or C₁-C₄ alkyl,wherein the alkyl may be optionally substituted with 1 to 3 substituentsindependently selected from halogen and C₁-C₃ alkoxy; R₇ is hydrogen,C₁-C₅ alkyl, C₃-C₇ cycloalkyl, (C₁-C₃ alkyl)₃ silyl, phenyl orthiophenyl, wherein the alkyl and cycloalkyl may be optionallysubstituted with one to three substituents independently selected fromhalogen, cyano, C₁-C₃ alkyl, C₁-C₃ alkoxy and C₁-C₃ alkylthio, andwherein the phenyl and thiophenyl may be optionally substituted with oneto three substituents independently selected from halogen, C₁-C₃ alkyl,C₁-C₃ haloalkyl and C₁-C₃ alkoxy; A is a direct bond or C(R₈)(R₉); R₈and R₉ are independently selected from hydrogen, fluoro and methyl; or asalt, enantiomer or N-oxide thereof, provided the compound is not


2. The compound, or a salt, enantiomer or N-oxide thereof, according toclaim 1 wherein R₁ is hydrogen, fluoro, chloro, methyl or cyano.
 3. Thecompound, or a salt, enantiomer or N-oxide thereof, according to claim 1wherein R₂ is hydrogen, methyl, chloro or fluoro.
 4. The compound, or asalt, enantiomer or N-oxide thereof, according to claim 1 wherein R₃ andR₄ are each independently selected from hydrogen and methyl.
 5. Thecompound, or a salt, enantiomer or N-oxide thereof, according to claim 1wherein R₅ is C₁-C₆ alkyl, C₂-C₆ alkenyl, cyclopropyl or C₃-C₄cycloalkyl-CH₂—, wherein the alkyl, alkenyl and cycloalkyl groups may beoptionally substituted with 1 to 3 substituents independently selectedfrom fluoro, chloro and methyl.
 6. The compound, or a salt, enantiomeror N-oxide thereof, according to claim 1 wherein R₆ is hydrogen or C₁-C₂alkyl, wherein the alkyl may be optionally substituted with 1 to 3substituents independently selected from fluoro and methoxy.
 7. Thecompound, or a salt, enantiomer or N-oxide thereof, according to claim 1wherein A is a direct bond or CH₂.
 8. The compound, or a salt,enantiomer or N-oxide thereof, according to claim 1 wherein R₇ is C₁-C₄alkyl, C₃-C₆ cycloalkyl, phenyl or thiophenyl, wherein the alkyl andcycloalkyl may be optionally substituted with one to three substituentsindependently selected from fluoro, chloro, methyl and methoxy, andwherein the phenyl and thiophenyl may be optionally substituted with oneto three substituents independently selected from fluoro, chloro,trifluoromethyl, methyl and methoxy and A is a direct bond; or,alternatively, R₇ is C₁-C₄ alkyl, C₃-C₆ cycloalkyl, trimethylsilyl,phenyl or thiophenyl, wherein the alkyl and cycloalkyl may be optionallysubstituted with one to three substituents independently selected fromfluoro, chloro, methyl and methoxy, and wherein the phenyl andthiophenyl may be optionally substituted with one to three substituentsindependently selected from fluoro, chloro, trifluoromethyl, methyl andmethoxy and A is CH₂.
 9. The compound, or a salt, enantiomer or N-oxidethereof, according to claim 1 wherein R₁ is hydrogen, fluoro, chloro ormethyl; R₂ is hydrogen, chloro or fluoro; R₃ is methyl and R₄ ishydrogen; or R₃ is hydrogen and R₄ is methyl; or R₃ is hydrogen and R₄is hydrogen; R₅ is C₁-C₅ alkyl, C₂-C₄ alkenyl, cyclopropyl or C₃-C₄cycloalkyl-CH₂—, wherein the alkyl, alkenyl and cycloalkyl groups may beoptionally substituted with 1 to 3 fluoro or one methyl; and R₆ ishydrogen, methyl or ethyl.
 10. The compound according to claim 1 whereinX is O or S; R₁ is hydrogen, fluoro, chloro or methyl; R₂ is hydrogen,chloro or fluoro; R₃ is methyl and R₄ is hydrogen; or R₃ is hydrogen andR₄ is methyl; or R₃ is hydrogen and R₄ is hydrogen; R₅ is C₁-C₅ alkyl,C₂-C₄ alkenyl, cyclopropyl or C₃-C₄ cycloalkyl-CH₂—, wherein the alkyl,alkenyl and cycloalkyl groups may be optionally substituted with 1 to 3fluoro or one methyl; R₆ is hydrogen methyl or ethyl; A is a direct bondand R₇ is phenyl or thiophenyl, wherein the phenyl and thiophenyl may beoptionally substituted with one to three substituents independentlyselected from fluoro, chloro and methyl; or, alternatively, A is CH₂ andR₇ is C₁-C₄ alkyl, cyclopropyl, cyclobutyl, phenyl or thiophenyl,wherein the alkyl cyclopropyl and cyclobutyl may be optionallysubstituted with one to three fluoro substituents or one methyl; or asalt, enantiomer or N-oxide thereof.
 11. The compound according to claim1 wherein X is O or S; R₁ is fluoro, chloro or methyl; R₂ is hydrogen orfluoro; R₃ and R₄ are both hydrogen; R₆ is hydrogen or methyl; A is adirect bond and R₅ is ethyl, isopropyl, tert-butyl, isopropenyl orcyclopropyl, wherein the ethyl, isopropyl and cyclopropyl groups may beoptionally substituted with 1 to 3 fluoro or one methyl and R₇ is phenylor thiophenyl; or, alternatively, A is CH₂ and R₅ is ethyl, propyl,isobutyl, neo-pentyl, C₃-C₄ alkenyl or cyclopropyl-CH₂—, wherein theethyl, propyl, isobutyl, neo-pentyl, C₃-C₄ alkenyl and cyclopropylgroups may be optionally substituted with 1 to 3 fluoros or one methyland R₇ is methyl, ethyl, isopropyl, cyclopropyl or cyclobutyl, whereinthe methyl, ethyl, isopropyl, cyclopropyl and cyclobutyl may beoptionally substituted with one to three fluoro substituents or onemethyl; or a salt, enantiomer or N-oxide thereof.
 12. The compound, or asalt, enantiomer or N-oxide thereof, according to claim 1 wherein X isO.
 13. A composition comprising a fungicidally effective amount of acompound of formula (I) as defined in claim
 1. 14. The compositionaccording to claim 13, wherein the composition further comprises atleast one additional active ingredient and/or a diluent.
 15. A method ofcombating, preventing or controlling phytopathogenic fungi whichcomprises applying to phytopathogenic fungi, to the locus ofphytopathogenic fungi, or to a plant susceptible to attack byphytopathogenic fungi, or to propagation material thereof, afungicidally effective amount of a compound of formula (I) as defined inclaim 1 or a composition comprising a fungicidally effective amount of acompound of formula (I) as defined in claim
 1. 16. A compound selectedfrom the group consisting of: N-[4-cyclopropyl-1-methyl-1-(2,2,2-trifluoroethyl)but-3-ynyl]-8-fluoro-quinoline-3-carboxamide;8-fluoro-N-(1-isobutyl-1-methyl-but-3-ynyl)quinoline-3-carboxamide;N-(1-isopropyl-3-phenyl-prop-2-ynyl)-8-methyl-quinoline-3-carboxamide;8-chloro-N-(1-isopropyl-3-phenyl-prop-2-ynyl)quinoline-3-carboxamide;8-fluoro-N-(1-isopropyl-3-phenyl-prop-2-ynyl)quinoline-3-carboxamide;8-fluoro-N-[4,4,4-trifluoro-1-(2-phenylethynyl)butyl]quinoline-3-carboxamide;N-(1-tert-butyl-3-phenyl-prop-2-ynyl)-8-fluoro-quinoline-3-carboxamide;N-(1,1-diethyl-3-phenyl-prop-2-ynyl)-8-fluoro-quinoline-3-carboxamide;N-[1,3-dimethyl-1-(2-phenylethynyl)butyl]-8-fluoro-quinoline-3-carboxamide;N-(1-ethyl-1-methyl-3-phenyl-prop-2-ynyl)-8-methyl-quinoline-3-carboxamide;8-cyano-N-(1-ethyl-1-methyl-3-phenyl-prop-2-ynyl)quinoline-3-carboxamide;8-chloro-N-(1-ethyl-1-methyl-3-phenyl-prop-2-ynyl)quinoline-3-carboxamide;8-fluoro-N-[3-(2-fluorophenyl)-1-i sopropyl-1-methyl-prop-2-ynyl]quinoline-3-carboxamide;8-fluoro-N-[1-isopropyl-1-methyl-3-(o-tolyl)prop-2-ynyl]quinoline-3-carboxamide;N-[1-ethyl-1-methyl-3-(o-tolyl)prop-2-ynyl]-8-fluoro-2-methyl-quinoline-3-carboxamide;N-[1-ethyl-1-methyl-3-(o-tolyl)prop-2-ynyl]-8-fluoro-quinoline-3-carboxamide;N-(1-ethyl-1-methyl-3-phenyl-prop-2-ynyl)-8-fluoro-2-methyl-quinoline-3-carboxamide;N-(1-ethyl-1-methyl-3-phenyl-prop-2-ynyl)-8-fluoro-quinoline-3-carboxamide;8-fluoro-N-[3-(2-fluorophenyl)-1,1-dimethyl-prop-2-ynyl]quinoline-3-carboxamide;N-[3-(5-cyano-2-methyl-phenyl)-1,1-dimethyl-prop-2-ynyl]-8-fluoro-quinoline-3-carboxamide;N-[3-(3,4-difluorophenyl)-1,1-dimethyl-prop-2-ynyl]-8-fluoro-quinoline-3 -carboxamide;N-[1,1-dimethyl-3-(p-tolyl)prop-2-ynyl]-8-fluoro-quinoline-3-carboxamide;N-[3-(2,5-dimethylphenyl)-1,1-dimethyl-prop-2-ynyl]-8-fluoro-quinoline-3-carboxamide;N-[3-(5-chloro-2-methoxy-phenyl)-1,1-dimethyl-prop-2-ynyl]-8-fluoro-quinoline-3-carboxamide;8-fluoro-N-[3-(5-fluoro-2-methyl-phenyl)-1,1-dimethyl-prop-2-ynyl]quinoline-3-carboxamide;N-[3-(2,4-difluorophenyl)-1,1-dimethyl-prop-2-ynyl]-8-fluoro-quinoline-3-carboxamide;N-[3-(2,3-dimethylphenyl)-1,1-dimethyl-prop-2-ynyl]-8-fluoro-quinoline-3-carboxamide;8-fluoro-N-[3-(4-fluorophenyl)-1,1-dimethyl-prop-2-ynyl]quinoline-3-carboxamide;8-fluoro-N-[3-(4-methoxyphenyl)-1,1-dimethyl-prop-2-ynyl]quinoline-3-carboxamide;8-fluoro-N-[3-(3-methoxyphenyl)-1,1-dimethyl-prop-2-ynyl]quinoline-3-carboxamide;N-[3-(3,5-dimethylphenyl)-1,1-dimethyl-prop-2-ynyl]-8-fluoro-quinoline-3-carboxamide;N-[3-(2-cyano-5-methyl-phenyl)-1,1-dimethyl-prop-2-ynyl]-8-fluoro-quinoline-3-carboxamide;N-[3-(3,4-dimethylphenyl)-1,1-dimethyl-prop-2-ynyl]-8-fluoro-quinoline-3-carboxamide;N-[3-(2,4-dimethylphenyl)-1,1-dimethyl-prop-2-ynyl]-8-fluoro-quinoline-3-carboxamide;N-[3-(4-cyano-2-methyl-phenyl)-1,1-dimethyl-prop-2-ynyl]-8-fluoro-quinoline-3-carboxamide;N-[1,1-dimethyl-3-(5-methyl-2-thienyl)prop-2-ynyl]-8-fluoro-quinoline-3-carboxamide;N-[3-(3-cyanophenyl)-1,1-dimethyl-prop-2-ynyl]-8-fluoro-quinoline-3-carboxamide;8-fluoro-N-[3-(2-methoxyphenyl)-1,1-dimethyl-prop-2-ynyl]quinoline-3-carboxamideN-[3-(4-chloro-3-methoxy-phenyl)-1,1-dimethyl-prop-2-ynyl]-8-fluoro-quinoline-3-carboxamide;N-[1,1-dimethyl-3-(m-tolyl)prop-2-ynyl]-8-fluoro-quinoline-3-carboxamide;N-[3-(3,5-difluorophenyl)-1,1-dimethyl-prop-2-ynyl]-8-fluoro-quinoline-3-carboxamide;N-[3-(2-cyanophenyl)-1,1-dimethyl-prop-2-ynyl]-8-fluoro-quinoline-3-carboxamide;N-[1,1-dimethyl-3-[4-(trifluoromethyl)phenyl]prop-2-ynyl]-8-fluoro-quinoline-3-carboxamide;8-fluoro-N-[3-2-methoxy-5-(trifluoromethyl)phenyl]-1,1-dimethyl-prop-2-ynyl]quinoline-3-carboxamide;8-fluoro-N-[3-(3-fluoro-4-methoxy-phenyl)-1,1-dimethyl-prop-2-ynyl]quinoline-3-carboxamide;8-fluoro-N-[3-(2-fluoro-5-methyl-phenyl)-1,1-dimethyl-prop-2-ynyl]quinoline-3-carboxamide;8-fluoro-N-(1-isopropyl-1-methyl-3-phenyl-prop-2-ynyl)quinoline-3-carboxamide;N-[1,1-dimethyl-3-(o-tolyl)prop-2-ynyl]-8-fluoro-quinoline-3-carboxamide;N-[1,1-dimethyl-3-[3-(trifluoromethyl)phenyl]prop-2-ynyl]-8-fluoro-quinoline-3-carboxamide;N-(1,1-dimethyl-3-phenyl-prop-2-ynyl)quinoline-3-carboxamide;N-(1,1-dimethyl-3-phenyl-prop-2-ynyl)-8-fluoro-2-methyl-quinoline-3-carboxamide;N-(1,1-dimethyl-3-phenyl-prop-2-ynyl)-8-fluoro-4-methyl-quinoline-3-carboxamide;8-fluoro-N-(4-methoxy-1,1-dimethyl-but-2-ynyl)quinoline-3-carboxamide;N-(1,1-dimethylbut-2-ynyl)-8-fluoro-quinoline-3-carboxamide;N-(1,1-dimethylprop-2-ynyl)-8-fluoro-quinoline-3-carboxamide;N-(1,1-dimethyl-3-phenyl-prop-2-ynyl)-8-fluoro-quinoline-3-carboxamide;N-[(1R)-4-cyclopropyl-1-methyl-1-(2,2,2-trifluoroethyl)but-3-ynyl]-8-fluoro-quinoline-3-carboxamide;N-[(1S)-4-cyclopropyl-1-methyl-1-(2,2,2-trifluoroethyl)but-3-ynyl]-8-fluoro-quinoline-3-carboxamide;8-fluoro-N-[(1R)-3-methyl-1-(2-phenylethynyl)butyl]quinoline-3-carboxamide;8-fluoro-N-[(1S)-3-methyl-1-(2-phenylethynyl)butyl]quinoline-3-carboxamide;N-[(1S)-1,3-dimethyl-1-(2-phenylethynyl)butyl]-8-fluoro-quinoline-3-carboxamide;N-[(1R)-1,3-dimethyl-1-(2-phenylethynyl)butyl]-8-fluoro-quinoline-3-carboxamide;8-fluoro-N-[(1S)-1-isopropyl-1-methyl-3-phenyl-prop-2-ynyl]quinoline-3-carboxamide;and8-fluoro-N-[(1R)-1-isopropyl-1-methyl-3-phenyl-prop-2-ynyl]quinoline-3-carboxamide.17. The compound of claim 16, wherein the compound is selected from thegroup consisting of:N-[4-cyclopropyl-1-methyl-1-(2,2,2-trifluoroethyl)but-3-ynyl]-8-fluoro-quinoline-3-carboxamide;and 8-fluoro-N-(1-isobutyl-1-methyl-but-3-ynyl)quinoline-3-carboxamide.18. The compound of claim 16, wherein the compound is selected from thegroup consisting of:N-(1-isopropyl-3-phenyl-prop-2-ynyl)-8-methyl-quinoline-3-carboxamide;8-chloro-N-(1-isopropyl-3-phenyl-prop-2-ynyl)quinoline-3-carboxamide;8-fluoro-N-(1-isopropyl-3-phenyl-prop-2-ynyl)quinoline-3-carboxamide;8-fluoro-N-[4,4,4-trifluoro-1-(2-phenylethynyl)butyl]quinoline-3-carboxamide;N-(1-tert-butyl-3-phenyl-prop-2-ynyl)-8-fluoro-quinoline-3-carboxamide;N-(1,1-diethyl-3-phenyl-prop-2-ynyl)-8-fluoro-quinoline-3-carboxamideN-[1,3-dimethyl-1-(2-phenylethynyl)butyl]-8-fluoro-quinoline-3-carboxamide;N-(1-ethyl-1-methyl-3-phenyl-prop-2-ynyl)-8-methyl-quinoline-3-carboxamide;8-cyano-N-(1-ethyl-1-methyl-3-phenyl-prop-2-ynyl)quinoline-3-carboxamide;8-chloro-N-(1-ethyl-1-methyl-3-phenyl-prop-2-ynyl)quinoline-3-carboxamide;8-fluoro-N-[3-(2-fluorophenyl)-1-isopropyl-1-methyl-prop-2-ynyl]quinoline-3-carboxamide;8-fluoro-N-[1-isopropyl-1-methyl-3-(o-tolyl)prop-2-ynyl]quinoline-3-carboxamide;N-[1-ethyl-1-methyl-3-(o-tolyl)prop-2-ynyl]-8-fluoro-2-methyl-quinoline-3-carboxamide;N-[1-ethyl-1-methyl-3-(o-tolyl)prop-2-ynyl]-8-fluoro-quinoline-3-carboxamide;N-(1-ethyl-1-methyl-3-phenyl-prop-2-ynyl)-8-fluoro-2-methyl-quinoline-3-carboxamide;N-(1-ethyl-1-methyl-3-phenyl-prop-2-ynyl)-8-fluoro-quinoline-3-carboxamide; 8-fluoro-N-[3 -(2-fluorophenyl)-1,1-dimethyl-prop-2-ynyl]quinoline-3-carboxamide;N-[3-(5-cyano-2-methyl-phenyl)-1,1-dimethyl-prop-2-ynyl]-8-fluoro-quinoline-3-carboxamide; N-[3 -(3,4-difluorophenyl)-1,1-dimethyl-prop-2-ynyl]-8-fluoro-quinoline-3-carboxamide;N-[1,1-dimethyl-3-(p-tolyl)prop-2-ynyl]-8-fluoro-quinoline-3-carboxamide;N-[3-(2,5-dimethylphenyl)-1,1-dimethyl-prop-2-ynyl]-8-fluoro-quinoline-3-carboxamide;N-[3-(5-chloro-2-methoxy-phenyl)-1,1-dimethyl-prop-2-ynyl]-8-fluoro-quinoline-3-carboxamide;8-fluoro-N-[3-(5-fluoro-2-methyl-phenyl)-1,1-dimethyl-prop-2-ynyl]quinoline-3-carboxamide;N-[3-(2,4-difluorophenyl)-1,1-dimethyl-prop-2-ynyl]-8-fluoro-quinoline-3-carboxamide; N-[3-(2,3-dimethylphenyl)-1,1-dimethyl-prop-2-ynyl]-8-fluoro-quinoline-3-carboxamide; 8-fluoro-N-[3-(4-fluorophenyl)-1,1-dimethyl-prop-2-ynyl]quinoline-3-carboxamide;8-fluoro-N-[3-(4-methoxyphenyl)-1,1-dimethyl-prop-2-ynyl]quinoline-3-carboxamide;8-fluoro-N-[3-(3-methoxyphenyl)-1,1-dimethyl-prop-2-ynyl]quinoline-3-carboxamide;N-[3-(3,5-dimethylphenyl)-1,1-dimethyl-prop-2-ynyl]-8-fluoro-quinoline-3-carboxamide; N-[3-(2-cyano-5-methyl-phenyl)-1,1-dimethyl-prop-2-ynyl]-8-fluoro-quinoline-3-carboxamide;N-[3-(3,4-dimethylphenyl)-1,1-dimethyl-prop-2-ynyl]-8-fluoro-quinoline-3-carboxamide;N-[3-(2,4-dimethylphenyl)-1,1-dimethyl-prop-2-ynyl]-8-fluoro-quinoline-3-carboxamide;N-[3-(4-cyano-2-methyl-phenyl)-1,1-dimethyl-prop-2-ynyl]-8-fluoro-quinoline-3-carboxamide;N-[1,1-dimethyl-3-(5-methyl-2-thienyl)prop-2-ynyl]-8-fluoro-quinoline-3-carboxamide; N-[3 -(3-cyanophenyl)-1,1-dimethyl-prop-2-ynyl]-8-fluoro-quinoline-3-carboxamide;8-fluoro-N-[3-(2-methoxyphenyl)-1,1-dimethyl-prop-2-ynyl]quinoline-3-carboxamide;N-[3-(4-chloro-3-methoxy-phenyl)-1,1-dimethyl-prop-2-ynyl]-8-fluoro-quinoline-3-carboxamide;N-[1,1-dimethyl-3-(m-tolyl)prop-2-ynyl]-8-fluoro-quinoline-3-carboxamide;N-[3-(3,5-difluorophenyl)-1,1-dimethyl-prop-2-ynyl]-8-fluoro-quinoline-3-carboxamide;N-[3-(2-cyanophenyl)-1,1-dimethyl-prop-2-ynyl]-8-fluoro-quinoline-3-carboxamide;N-[1,1-dimethyl-3-[4-(trifluoromethyl)phenyl]prop-2-ynyl]-8-fluoro-quinoline-3-carboxamide;8-fluoro-N-[3-[2-methoxy-5-(trifluoromethyl)phenyl]-1,1-dimethyl-prop-2-ynyl]quinoline-3-carboxamide; 8-fluoro-N-[3 -(3-fluoro-4-methoxy-phenyl)-1,1-dimethyl-prop-2-ynyl]quinoline-3-carboxamide;8-fluoro-N-[3-(2-fluoro-5-methyl-phenyl)-1,1-dimethyl-prop-2-ynyl]quinoline-3-carboxamide;8-fluoro-N-(1-isopropyl-1-methyl-3-phenyl-prop-2-ynyl)quinoline-3-carboxamide;N-[1,1-dimethyl-3-(o-tolyl)prop-2-ynyl]-8-fluoro-quinoline-3-carboxamide;N-[1,1-dimethyl-3-[3-(trifluoromethyl)phenyl]prop-2-ynyl]-8-fluoro-quinoline-3-carboxamide;N-(1,1-dimethyl-3-phenyl-prop-2-ynyl)quinoline-3-carboxamide;N-(1,1-dimethyl-3-phenyl-prop-2-ynyl)-8-fluoro-2-methyl-quinoline-3-carboxamide;N-(1,1-dimethyl-3-phenyl-prop-2-ynyl)-8-fluoro-4-methyl-quinoline-3-carboxamide;8-fluoro-N-(4-methoxy-1,1-dimethyl-but-2-ynyl)quinoline-3-carboxamide;N-(1,1-dimethylbut-2-ynyl)-8-fluoro-quinoline-3-carboxamide;N-(1,1-dimethylprop-2-ynyl)-8-fluoro-quinoline-3-carboxamide; andN-(1,1-dimethyl-3-phenyl-prop-2-ynyl)-8-fluoro-quinoline-3-carboxamide.19. The compound of claim 16, wherein the compound is selected from thegroup consisting of:N-[(1R)-4-cyclopropyl-1-methyl-1-(2,2,2-trifluoroethyl)but-3-ynyl]-8-fluoro-quinoline-3-carboxamide;N-[(1S)-4-cyclopropyl-1-methyl-1-(2,2,2-trifluoroethyl)but-3-ynyl]-8-fluoro-quinoline-3-carboxamide;8-fluoro-N-[(1R)-3-methyl-1-(2-phenylethynyl)butyl]quinoline-3-carboxamide;8-fluoro-N-[(1S)-3-methyl-1-(2-phenylethynyl)butyl]quinoline-3-carboxamide;N-[(1S)-1,3-dimethyl-1-(2-phenylethynyl)butyl]-8-fluoro-quinoline-3-carboxamide; N-[(1R)-1,3-dimethyl-1-(2-phenylethynyl)butyl]-8-fluoro-quinoline-3-carboxamide;8-fluoro-N-[(1S)-1-isopropyl-1-methyl-3-phenyl-prop-2-ynyl]quinoline-3-carboxamide; and 8-fluoro-N-[(1R)-1 sopropyl- 1-methyl-3-phenyl-prop-2-ynyl]quinoline-3-carboxamide.